Nos objectifs sont ici de comprendre comment les propriétés magnétiques de nanoparticules (NPs) sont affectées par la diminution de leur taille et par leur composition chimique, et comprendre ce qui régit leur mouvement thermophorétique et l'effet magnéto-calorique. Des ferrofluides composés de NPs de structure cœur-couronne sont synthétisés ici avec un cœur de ferrite de Mn, de Co ou de ferrite mixte Zn-Mn, recouvert d'une couronne de maghémite. Les mesures magnétiques révèlent une composition magnétique mixte conduisant à l'observation d'un exchange bias qui se manifeste par des cycles d'hystérésis décalés à basses températures. Nous comparons ce phénomène dans le cas de NPs à cœur magnétiquement dur (CoFe2O4) et à cœur magnétiquement mou (MnFe2O4). Indépendamment de la nature du cœur, ce champ d'échange augmente jusqu'à un maximum, obtenu quand le champ de refroidissement est de l'ordre de la moitié du champ d'anisotropie. Les propriétés thermophorétiques des dispersions, sondées par diffusion Rayleigh forcée, sont gouvernées par la physico-chimie du colloïde (ligand de surface, contre-ions, interactions entre NPs) indépendamment de la composition chimique et des propriétés magnétiques en champ nul. Le coefficient Soret est ici négatif (NPs thermophiles) et est relié à la compressibilité osmotique donnée par un formalisme de Carnahan-Starling effectif. On modélise la friction en régime dilué par la loi d'Einstein et en régime concentré, à l'approche de la transition vitreuse, par un modèle de Vogel-Fulcher. Les mesures de l’effet magnéto-calorique démontrent une similarité avec les matériaux commerciaux, avec une forte influence de la composition chimique du cœur. / Our objective is to understand how the magnetic properties of nanoparticles (NPs) can be affected by their size reduction and their chemical composition, and also to determine their role on their thermophoretic motion and on the magneto-caloric effect. For this purpose, aqueous ferrofluids are synthesized with core-shell NPs based on a core of Mn-ferrite, Co-ferrite and mixed Zn-Mn ferrites, coated with a maghemite shell. The magnetic measurements evidence a ferrimagnetic core, covered with disordered frozen spins (SGL), driving an exchange bias phenomenon shifting the hysteresis loops, when the system is cooled under a field Hfc. This exchange bias is measured as a function of Hfc, in samples with NPs having either a hard (CoFe2O4) or a soft (MnFe2O4) magnetic core. Whatever the nature of the magnetic core, the exchange bias field grows up to reach a maximum, always found at Hfc of the order of half of the anisotropy field. The thermophoretic properties of the dispersions, probed by Forced Rayleigh Scattering, are ruled by colloidal physico-chemical features (surface ligand, counter ions, interparticle interactions) whatever the chemical composition and the magnetic properties in zero magnetic field. The Soret coefficient is found here negative (thermophilic NPs) and is related to the osmotic compressibility, modeled by an effective Carnahan-Staring formalism. In the dilute regime, the friction follows an Einstein law, while a Vogel-Fulcher formalism describes the concentrated regime, at the approach of the glass transition. The magneto-caloric measurements demonstrate a similarity with commercial materials. They are strongly influenced by the core composition.

This diploma thesis is focused on investigation of metallic thin films and nanostructures using scanning probe microscopy. Magnetic properties of these objects are studied by magnetic force microscopy, which is modification of scanning probe microscopy. In the theoretical part basic principles of scanning probe microscopy and magnetic force microscopy are summarized, and also principle of creation of magnetic domains and some special properties of ferromagnetic and antiferromagnetic materials. Further, two techniques of fabricating nanostructures are described. Experimental part is focused on imaging and simulating of magnetic domains. Further, exchange bias is revealed. This phenomenon is present in systems composed from ferromagnetic and antiferromagnetic materials. One part of this diploma thesis is also focused on discussion of problems with magnetic force microscopy.

The present work covers the fabrication and electrical and magnetic investigation of LaNiO3- and LaMnO3- based superlattices (SL). In recent years, several interesting theoretical predictions have been made in these SLs, for example, Mott insulators, metal-insulator transitions, superconductivity, topological insulators, and Chern insulators. Motivated by the promising theoretical predictions, four kinds of SLs with different designed structures and orientations were systematically studied in this thesis. The samples were grown by pulsed laser deposition with in-situ reflection high-energy electron diffraction to monitor the two-dimensional layer-by-layer growth process. In order to ensure the high-quality of SLs, growth parameters were optimised. Characteristic methods like X-ray diffraction, atomic force microscopy, and transmission electron microscopy were used. These measurements proved the high-quality of the SLs and provided the basis for electrical and magnetic measurements. The first studied SL is the (001)-oriented LaNiO3/LaAlO3 SL, which was predicted as a superconductor in theory. Temperature-dependent resistivity measurements revealed a metal-insulator transition by lowering the dimensionality of the LaNiO3 layers in the SLs from three dimensions to two dimensions. The second studied SL is the (111)-oriented LaNiO3/LaAlO3 SL, which was predicted as a topological insulator in theory. The polarity-controlled conductivity was observed and the intrinsic conductivity mechanisms were discussed by means of appropriate modeling. The third studied SL is LaMnO3/LaAlO3 SL, which was predicted as a Chern insulator in theory. By lowering the temperature, a paramagnetic-ferromagnetic phase transition and a thermal activated behavior were observed in the SLs. The last studied SL is the LaNiO3/LaMnO3 SL, in which an exchange bias effect was expected. The studies reveal the exchange bias exists in three kinds of SLs with different orientations.

No description available.

The process of assembling metal nanoparticles at the interface of two liquids has received a great interest over the past few years due to a wide range of important applications and their unusual properties compared to bulk materials. The work in this thesis presents a low cost, simple and cheap synthesis of metal nanoparticles, core/shell structures and semiconductors followed by assembly of these particles between immiscible liquids. The aim of this thesis is divided to three parts (Summary of the experimental work of this thesis is in Table A1):1) To achieve a closed loop recycling for producing cadmium sulfide as powders and/or nanostructured thin films for solar cells or other optoelectronic devices applications. A series of bis(dialkyldithiocarbamato)cadmium(II) were used for this approach. Bis(dioctyldithiocarbamato)cadmium(II) complexes proved to be the optimal alkyl chain for this process. The approach can be extended to other metal sulfides such as those of Zn, Pb, Cu, or Fe and many transition metals and oxides.2) To explore the phenomena of exchange bias in very small size particles (5 nm) of Ni/NiO (core/shell structure) obtained by solution phase synthesis. Ferromagnetism (FM) due to exchange bias is well established in the case of larger particles with diameters over 10 nm. However, sub 10 nm magnetic structures synthesized by solution phase have never been found to be ferromagnetic at room temperature. These Ni/NiO nanocrystals with ferromagnetic properties at room temperature were among the smallest and strongest magnets made in solution. Similar magnets can be obtained using a rare class of high anisotropy materials nearly all of which feature precious metals. This work would lead to significantly cheaper magnetic particles suited for the mass market. The applications of this work can be applied to produce viable storage devices and the other possibility is to disperse these nanocrystals in solution and use it to make ferrofluids which have a number of mature applications. Functional device architectures of these particles were rapidly and inexpensively produced as thin films using self-assembly of liquid/liquid interface process at room temperature by using octylamine as a surfactant.3) To synthesise and assemble submicron particles of silver, cobalt and nickel by using polyol methods and liquid/liquid interface, respectively. The effect of reaction conditions (solvent, precursor concentration, temperature, etc.) on synthesis and assembly of the particles was studied. Assembled cobalt and nickel as films are promising materials for spintronics, magnetic and magneto-electronics and biomedics. The nature and characteristics of the particles and their films were studied by a number of techniques such as SEM, EDX, TEM, p-XRD, UV-Vis, PL, FTIR, DLS and SQUID for magnetic measurements.

The potentially most important challenges today are related to energy and the environment. New materials and methods are needed in order to, in a sustainable way, convert and store energy, reduce pollution, and clean the air and water from contaminations. In this, nanomaterials and nanocomposites play a key role, and hence knowledge about the relation between synthesis, structure, and properties of nanosystems is paramount. This thesis demonstrates that solution-chemical synthesis, using amine-modified acetates and nitrates, can be used to prepare widely different nanostructured films. By adjusting the synthesis parameters, metals, oxides, and metal–oxide or oxide–oxide nanocomposites were prepared for two systems based on Co and Zn:Fe, respectively, and the films were characterised using diffraction, spectroscopy, and microscopy techniques, and SQUID magnetometry. A variety of crystalline cobalt films—Co metal, CoO, Co3O4, and composites with different metal:oxide ratios—were synthesised. Heat-treatment parameters and control of the film thickness enabled tuning of the phase ratios. Random and layered Co–CoO composites were prepared by utilising different heating rates and gas flow rates together with a morphology effect associated with the furnace tube. The Co–CoO films exhibited exchange bias due to the ferromagnetic–antiferromagnetic interaction between the Co and CoO, whereas variations in e.g. coercivity and exchange bias field were attributed to differences in the structure and phase distribution. Ordered structures of wurtzite ZnO surrounded by amorphous ZnxFeyO were prepared through controlled phase segregation during the heating, which after multiple coating and heating cycles yielded ZnO–ZnxFeyO superlattices. The amorphous ZnxFeyO was a prerequisite for superlattice formation, and it profoundly affected the ZnO phase, inhibiting grain growth and texture, already from 1% Fe. In addition, ZnO–ZnxFeyO exhibited a photocatalytic activity for the oxidation of water that was higher than results reported for pure ZnO, and comparable to recent results reported for graphene-modified ZnO.

Dans le cadre de l’étude des phénomènes magnétiques et de la spintronique qui sont présents aux échelles nanoscopiques nous avons étudié différents aspects des structures asymétriques de Pt/Co/AlOx. L’un des objectifs de cette thèse est le contrôle de l’oxydation et des propriétés magnétiques de ces multicouches. Nous avons combiné les mesures de structures (réflexion de Rayon-X), transports (Effet Hall anormal), et magnétiques (VSM-SQUID) afin de déterminer les rôles des effets magnétiques et d’interfaces. Un objectif était d’analyser le rôle de quelques monocouches (MCs) de CoO (qui peut se former lors de la sur oxydation de l’Al) sur les propriétés de la multicouche. Nous avons utilisé une technique de déposition avec un gradient d’épaisseur pour contrôler l’oxydation à l’échelle nanométrique. Nous avons établis que quelques monocouches (MCs) de CoO a un impact sur l’anisotropie de a multicouche. Pour approfondir l’effet de la couche de CoO, nous avons construit des bicouches ultrafines de Co(0.6nm)/CoO(0.6nm). Nous avons effectué des mesures refroidi sur champ sur ce système et trouvé un fort effet de couplage d'échange. Ces résultats indiquent que la couche CoO garde une forte anisotropie même en dans la limite des monocouches et permet de réfuter certains modèles sur l’effet d’échange bias et indique que les couches, couramment négligé, de CoO doivent être prises en considération dans le bilan énergétiques du système. Nous avons construits un appareil de mesure perpendiculaire de la magnétorésistance tunnel anisotrope (TAMR) à partir de la structure Pt/Co/AlOx. La TAMR est un effet de spintronique relativement récent dans lequel la rotation d’aimantation dans une électrode magnétique (combiné avec un couplage spin-orbite) peut entrainer un changement de la probabilité de l’effet tunnel, ce qui se manifeste comme un effet de magnétorésistance. Nous avons démontré qu’un contrôle précis de l’état d’oxydation est essentiel pour l’effet TAMR. La forte anisotropie magnétique induite nous permet d’atteindre des valeurs de TAMR plus grande comparée à celle des structures Pt/Co/AlOx. / In the context of studying magnetic and spintronics phenomena occurring at the nanoscale, we investigated several aspects of Pt/Co/AlOx asymmetric structures. One of the objectives of this thesis was the control of the oxidation and the tailoring of the magnetic properties of these multilayers. We combined structural (X-Ray Reflectivity), transport (Anomalous Hall Effect) and magnetic measurements (VSM-SQUID), to study the interplay of magnetic and interfacial effects. One objective was to analyze the role that few monolayers (MLs) of CoO (which can form when overoxidizing the Al layer), could have on the properties of the stack. We used a wedge deposition techniques to control the oxidation on a subnanometer scale. We established that few MLs of CoO largely affect the total anisotropy of the stack. To further investigate the impact of the CoO, we engineered ultrathin Co(0.6nm)/CoO(0.6nm) bilayers. We performed field cooled measurements on this system and we found a large exchange bias anisotropy. These results indicate that the CoO keeps a large anisotropy even in the ML regime, help to rule out some of the models proposed to explain the exchange bias effect and imply that the usually neglected CoO presence must be considered in the energy balance of the system. We build perpendicular Tunneling Anisotropic MagnetoResistance (TAMR) devices based on the Pt/Co/AlOx structure. The TAMR is a relatively new spintronics effect in which the rotation of the magnetization in a single magnetic electrode (combined with the Spin-Orbit Coupling) can cause a change of the tunnel probability, which manifests as a magnetoresistance effect. We demonstrated that a careful control of the interface oxidation is crucial for the TAMR effect. The large induced magnetic anisotropy allowed us to achieve enhanced TAMR values compared to similar Pt/Co/AlOx structures.

La spintronique antiferromagnétique est un domaine de recherche émergent dans le secteur des technologies de l'information. Ce domaine exploite la combinaison unique de propriétés dans les matériaux antiferromagnétiques. Leur grande fréquence d'excitation, leur robustesse face à des champs extérieurs, une aimantation totale nulle et la possibilité de générer de forts effets de magnéto-transport les rendent particulièrement intéressants. Le transfert de spin, le couplage spin-orbite et les effets caloritroniques constituent les phénomènes qui ont façonné une grande partie de la recherche et des développements récents en spintronique. Dans cette thèse, nous avons étudié les effets de transfert et de pompage de spin dans des antiferromagnétiques métalliques et isolants au moyen de la technique de résonance ferromagnétique, dans des tricouches du type injecteur de spin ferromagnétique - NiFe, CoFeB / (conducteur de spin - Cu / absorbeur de spin antiferromagnétique - IrMn, NiFeOx, NiO. Les mesures de la dépendance en température de la relaxation ferromagnétique ont révélé un nouvel effet de pompage de spin associé aux fluctuations linéaires lors de la transition de phase magnétique de l'antiferromagnétique, quel que soit l'état électronique et la nature du transport de spin. Cela ouvre de nouvelles voies pour un pompage de spin plus efficace, tout en fournissant une méthode polyvalente pour mesurer la température critique des films ultra-minces à aimantation totale nulle. Dans le but de mesurer à la fois les fluctuations de spin linéaires et non linéaires dans l'antiferromagnétique, nous avons effectué des mesures électriques dans une configuration de mesure du type ‘spin Hall’. Une dépendance en température non-monotone inédite de la tension dc transverse a parfois été observée. Elle est principalement associée aux propriétés d’un ferromagnétique spécifique: le Permalloy, sans rapport avec les effets de rectification de spin. Ces résultats s'ajoutent à une littérature croissante sur l'absorption d’un courant de spin, soulignant la capacité des ferromagnétiques à agir comme détecteurs de courant de spin émis à la suite de phénomènes impliquant une dynamique d’aimantation. Finalement, nous avons utilisé le couplage d'échange pour étudier et ensuite façonner les propriétés magnétiques et électriques de plusieurs antiferromagnétiques destinés à diverses applications spintroniques, y compris la lecture par magnétorésistance tunnel anisotrope. / Antiferromagnetic spintronics is an emerging research field in the area of information technology that exploits the unique combination of properties of antiferromagnets. It is their high excitation frequency, robustness against external fields, zero net magnetization and possibility of generating large magneto-transport effects that makes them so interesting. Spin transfer, spin-orbit coupling and spin caloritronics constitute the phenomena that have shaped much of the recent research and development towards pure antiferromagnetic spintronics. Here we investigate spin transfer torque and spin pumping in both metallic and insulating antiferromagnets by means of ferromagnetic resonance technique, in ferromagnetic spin injector – NiFe, CoFeB / (spin conductor – Cu) / antiferromagnetic spin sink – IrMn, NiFeOx, NiO trilayers. Temperature dependence measurements of the ferromagnetic relaxation revealed a novel spin pumping effect associated to the linear fluctuations at the magnetic phase transition of the antiferromagnet, regardless its electronic state and the nature of the spin transport. This opens new ways towards more efficient spin pumping, while providing at the same time a versatile method to probe the critical temperature of ultrathin films with zero net magnetization. Next, in an effort to probe linear as well as non-linear fluctuations in the antiferromagnet we conducted electrical measurements in spin Hall geometry. A novel non-monotonous temperature dependence of transverse dc voltage was sometimes observed, mostly associated to the properties of a specific ferromagnet: Permalloy, unrelated to spin rectification effects. These findings add to a growing body of literature on spin current absorption, highlighting the ability of ferromagnets to act as spin current detectors, in phenomena involving magnetization dynamics. Finally, we used exchange bias to investigate and subsequently engineer the magnetic and electric properties of various antiferromagnets intended for diverse spintronic applications including reading via tunneling anisotropic magnetoresistance.

Nous nous proposons d'étudier l'interaction au niveau de l'interface entre un matériau antiferromagnétique et un ferromagnétique par un ensemble de techniques expérimentales qui utilisent le rayonnement synchrotron. Nous sommes particulièrement intéressés par l'effet de couplage d'échange dans les couches minces magnétiques avec anisotropie hors du plan. Les systèmes que nous avons étudiés sont les couches ordonnées chimiquement, FePt et MnPt sur Pt(001), et Fe/Ag(001), éventuellement couplée à CoO. Notre approche consiste à trouver de surfaces adaptées et d'étudier, pour chaque bicouche, la croissance individuelle de chaque élément, alliage ou oxyde. A travers le contrôle d'un certain nombre des paramètres, comme la structure de la surface, la propreté, le taux et la température de déposition, nous avons obtenus une bonne connaissance du processus de croissance. Les systèmes obtenus ont été étudiés in situ par la diffraction de surfaces et ex situ par l'effet Kerr magnéto-optique, le dichroïsme circulaire magnétique de rayons X et la spectroscopie d'absorption de rayons X. La relation entre le couplage d'échange, qui se manifeste par l'augmentation de la coercivité et par un champ de décalage, et la structure des couches est discutée pour les interfaces MnPt/FePt and CoO/Fe. / Our aim is to study the interaction of antiferromagnetic and ferromagnetic materials with well-defined interface by combining structural, electronic and magnetic techniques using synchrotron light. Our interest is guided by the exchange bias effect in thin ferromagnetic films with perpendicular magnetic anisotropy. The main systems studied in this work were ultra-thin layers of chemically-ordered alloys of FePt and MnPt on Pt(001) and of Fe/Ag(001), eventually coupled to CoO. Our strategy was to find an appropriate surface and, for each coupled bilayer, study the individual growth of each element, alloy or oxide. By controlling a variety of parameters, such as surface structure, cleanliness, deposition rate and temperature, we have got a good understanding of the growth process. The coupled systems obtained were studied in situ by grazing incidence X-ray diffraction and ex situ by magneto-optic Kerr effect, X-ray magnetic circular dichroism and X-ray absorption spectroscopy. The relation between the exchange coupling, which manifests itself by an increase in coercivity and a bias field, and the structural characteristics was discussed for the MnPt/FePt and CoO/Fe interfaces.Keywords: exchange bias, chemically ordered alloy, MnPt, FePt, Fe/Ag(001), surface X-ray diffraction, X-ray absorption, MOKE, synchrotron.

Made available in DSpace on 2014-06-12T18:01:29Z (GMT). No. of bitstreams: 2 arquivo2354_1.pdf: 6055782 bytes, checksum: 76375bee6f225ba09f816921ea89b485 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação desenvolvemos atividades de fabricação de filmes compostos de multicamadas magnéticas, caracterização de suas propriedades e interpretação fenomenológica dos resultados. Investigamos os efeitos de acoplamentos magnéticos que ocorrem em bicamadas do tipo ferromagneto/antiferromagneto (FM/AF) e em estruturas do tipo válvulas de spin, que são adequadas para investigar a superposição dos acoplamentos direto (exchange bias) e indireto (mediado pela camada não magnética). Todas as amostras investigadas neste trabalho foram fabricadas pela técnica de sputterin DC e RF e para caracterizar as propriedades estáticas e dinâmicas da magnetização utilizamos as técnicas de ressonância ferromagnética (FMR) e magnetoresistência (MR). As medidas de MR ao longo do eixo fácil permitiram medir a dependência do campo de exchange bias (HE) e do campo coercivo (HC) em função da temperatura. Ambos HE e HC mostram um crescimento monotônico à medida que a temperatura diminui. Para as medidas de ressonância ferromagnética levamos em consideração três diferentes mecanismos de relaxação para explicar a dependência angular da largura de linha em bicamadas FM/AF. A simetria das curvas H vs.H foi ajustada numericamente e verificamos a importância dos mecanismos de 2-mágnons e de flutuação dos eixos de anisotropia. Considerando as válvulas de spin, as análises de FMR mostraram a existência de dois picos de absorção correspondentes às ressonâncias das camadas livre e presa. Para espessuras grandes da camada separadora de rutênio, a camada livre apresenta uma dependência angular típica de um filme simples e a camada presa apresenta uma dependência típica de um acoplamento do tipo exchange bias. Para espessuras menores da camada de Ru verificamos o efeito da mudança do sinal do acoplamento indireto entre as camadas livre e presa. Estes resultados também foram confirmados pelas curvas de MR, obtidas ao longo do eixo de anisotropia e para diferentes espessuras da camada separadora. Medidas de ressonância ferromagnética feitas ao longo do eixo unidirecional com o campo aplicado paralelo e antiparalelo a direção de mínimo de energia, nos permitiram estudar o comportamento da largura de linha e do campo de ressonância em função da temperatura, fizemos também uma estimativa do campo de exchange bias para medidas de FMR em função da temperatura e comparamos os resultados com os obtidos por MR