Dissertations / Theses on the topic 'Nano-magnetism'

The transmission and effective magnetic properties of a metamaterial consisting of silver nanowires that we call a "silver nanoforest" was investigated using finite element numerical simulations in the optical regime. The variation of these properties with the arrangement and size of the nanowires was also investigated along with resilience to fabrication disorder. The silver nanoforest metamaterial exhibited low loss diamagnetism associated with Fabry Perot interference. In addition to diamagnetism both negative pelmeability and negative refractive index were obtained, but not simultaneously at same' wavelength and geometry. Both negative permeability and negative index experienced significant loss and therefore low transmission due to the plasmonic Origins of these effects. Magnetic responses of the silver nanoforest metamaterial were dampened but not inhibited by disorder, with diamagnetic response being the most resilient magnetic response to disorder.

The magnetic and structural properties of nano magnet arrays and ferromagnetic thin films are investigated. Circular x-rays are used and extensive use is made in this Thesis of the X-ray Magnetic Circular Dichroism (XMCD) technique. By means of the XMCD magneto-optic sum rules the values of the orbital and spin moments are determined. In the case of the nano magnet arrays studied, the XMCD technique is used in a spatially resolved mode using Photo Electron Emission Microscopy (PEEM) after circular light excitation. The Extended X-ray Absorption Fine Structure (EXAFS) is studied in both the Co K- and L-edges. In situ Co L-edge X-ray XMCD spectroscopy measurements are presented, in combination with spectro-microscopy results, on Co/Pt and Co/Au based nano-dot arrays, of typical dot lateral size 250×100 nm2, on self organized Si0.5Ge0.5. The Co is only a few atomic layers thick. The dot arrays display a high degree of lateral order and the individual dots, in several cases, exhibit a stable magnetic moment at 300 K. It is found possible to characterize the spin reorientation of these dot arrays. For both systems the in- versus out-of-plane orbital moment anisotropy, is not always related with an out-of-plane magnetization and the occurrence of a spin reorientation. By performing Co K-edge EXAFS measurements the local atomic structure around the Co atoms is characterized. The feasibility of a high precision quantitative structural analysis of L-EXAFS is studied on the system Au/Co/Au/W(110). The spin reorientation transition is studied as a function of the Co thickness and Au cap thickness. The L-edge EXAFS indicates that this reorientation is correlated to a lattice expansion in the perpendicular direction. High precision angle dependent XMCD work is performed on a high temperature exchange bias system. Pinned or frozen magnetic moments are studied within an exchange biased NiFe ferromagnet at the NiFe/FeMn, ferromagnet/antiferromagnet interface by XMCD and complemented by x-ray resonant reflectivity experiments, at the Ni, Fe and Mn L-edges. The Mn L-edge XMCD MnSb and of (Ga, Mn)As layers modified by high temperature annealing is studied. For MnSb an enhanced value is obtained versus theoretical calculations. This result can be explained by means of the enhanced surface to volume ratio for the samples studied. For (Ga, Mn)As differences are found in the local environment of the Mn atoms upon annealing.

Le nanomagnétisme est actuellement un champ d'investigation très actif grâce aux développements de méthodes de synthèse et d'investigation originales. Cette thèse s'attache à sonder le magnétisme de nanofils magnétiques synthétisés par un procédé polyol. Ce procédé présente l'avantage de fournir un large éventail d'objets magnétiques anisotropes présentant une très bonne qualité cristalline. Les nanofils ainsi synthétisés présentent des diamètres variant de 7nm à 20nm, leur conférant un mode de renversement de l'aimantation cohérent. Cette thèse montre que les nanofils ainsi synthétisés ont des coercivités élevées comparées à celles de nanofils synthétisés par d'autres voies. Par ailleurs, les effets de l'oxydation de ces nanofils sur leurs propriétés magnétiques ont été étudiés. Les mesures magnétiques ont révélé une dépendance en température des champs d'échange et coercitif inhabituelle. Cela a permis de mettre en lumière le rôle prépondérant des fluctuations superparamagnétiques des grains antiferromagnétiques d'oxyde de cobalt dans le phénomène d'Exchange Bias. Enfin, cette thèse a aussi pour objectif de développer la technique de Diffusion de Neutrons Polarisés aux Petits Angles pour sonder le magnétisme de nanofils. Jusqu'à présent, cette technique a été surtout réservée à l'étude d'objets magnétiques isotropes. En effet, l'alignement des nanofils est crucial pour extraire des informations quantitatives d'une telle étude. C'est pour cela, qu'outre les nanofils synthétisés par procédé polyol, des nanofils inclus dans des matrices d'alumine poreuse ont aussi été étudiés par cette technique
Magnetism of individual nano-objects is a very active research field thanks to the development of original synthesis routes and investigation tools. This thesis aims at probing the magnetism of nanowires synthesized via a pure chemical route, the polyol process. This process provides a large variety and an excellent crystallinity of the synthesized nanowires. This process allows to tune the diameter of the nanowires from 7nm to 20nm leading to coherent magnetization reversaI in the nanowires. I show how the large shape and magnetocrystalline anisotropies provide large coercivities compared to magnetic nanowires synthesized via other routes. Furthermore, the oxidation of such objects has also been investigated. Magnetic measurements has revealed unsual temperature dependencies of both the coercive and exchange fields, emphasizing the role of the superparamagnetic fluctuations of the CoO antiferromagnetic grains in the Exchange Bias effect. Finally, this thesis also aims at developing Polarized Small Angle Neutron Scattering to probe magnetism in complex nano-objects. Such a technique has been ignored until now to study magnetic anisotropic nano-objects despite being well adapted. The key ingredient to carry through such a study is the perfect alignment of the nanowires. This is why, besides the nanowires synthesized via the polyol process, Polarized Small Angle neutron Scattering measurements have been performed on arrays of magnetic nanowires included in porous alumina membranes

Atualmente, nanopartículas (NPs) são utilizadas em todos os ramos da tecnologia. Suas promissoras aplicações envolvem entre outros, o campo dos sensores e transdutores, mídia de gravação magnética, carreadores magnéticos de drogas medicinais. Com o objetivo de produzir NPs pelo método físico, um gerador de nanopartículas foi adaptado usando um dos canhões do sistema de magnetron sputtering, baseando-se no método de agregação gasosa. Com o gerador somos capazes de produzir NPs de diversos materiais e codepositá-las em matrizes dielétricas ou metálicas. Neste trabalho apresentamos o desenvolvimento da metodologia para a produção de nanopartículas de materiais magnéticos duros, usando alvos de SmCo5, Sm2Co17, Nd2Fe17B, FePt e CoPt. Investigamos a influência dos parâmetros de deposição (pressão, fluxo de gás e potência de sputtering), tipo de substrato e a existência de buffer e/ou codeposição, na obtenção das propriedades estruturais e magnéticas desejadas para esses materiais. As NPs produzidas são analisadas magneticamente pelo VSM e SQUID, sua morfologia e tamanho por TEM e SEM, a sua estequiometria pelo RBS, e a sua estrutura cristalina por XRD, a fim de obter nano-ímãs de alta anisotropia magnética. Da caracterização morfológica, através de microscopia eletrônica, encontramos para as NPs produzidas e estudadas diâmetros entre 5 e 17 nm. Através de análises de RBS obtemos para composição das NPs que as mesmas possuem estequiometria diferente dos alvos usados. Estudos estruturais e magnéticos mostram que para Sm-Co, Fe-Pt e Co-Pt é possível obter NPs cristalinas e com coercividade da ordem de 1 kOe.
In the recent years, nanoparticles (NPs) are being in all fields of technology. Their promising applications involve among others, the field of sensors and transducers, magnetic recording media, magnetic carriers of medicinal drugs. Aiming to produce NPs by physical method, a generator of nanoparticles was adapted using a system of guns \"magnetron sputtering\", based on the aggregation gas method. With the generator we are able to produce NPs with different types of material. In this work, we present the development of the methodology for the production of nanoparticles of hard magnetic materials, using targets of SmCo5, Sm2Co17, Nd2Fe17B, FePt and CoPt. We investigated the influence of the deposition parameters (pressure, gas flux and sputtering power), substrate type and the existence of the buffer and/or codeposition layers, to obtain the desired structural and magnetic properties for the nanoparticles. The produced NPs were magnetically analyzed by VSM and SQUID, the morphology and size by TEM and SEM, the stoichiometry by RBS and the crystal structure by XRD. The main objective of this work is to obtain nano-magnet with high magnetic anisotropy. Through the morphological characterization by electron microscopy, we found for NPs produced and studied have diameters between 5 and 17 nm. Through RBS analysis we have obtained the composition of the NPs, and also that they have different stoichiometry in relation to the used targets. Structural and magnetic studies have show that for Sm-Co, Fe-Pt and Co-Pt it is possible to obtain crystalline NPs with coercive field around 1 kOe.

Magnetic data storing has been of great interest since 1950 when the first magnetic hard drive was fabricated. A lot has happened since then, but there is still a need for smaller and cheaper devices.  One way to achieve this is by creating nano-sized ferromagnetic areas in a thin film at room temperature, or nano-magnets. In this thesis, the aim is to fabricate and characterize novel amorphous nano-magnets. Using a chromium mask ions can be implanted in a nano-sized pattern in an amorphous iron zirconium thin film. The mask is fabricated by depositing chromium over the iron zirconium and etching the nano-structures into the chromium film.  This requires the parameters for the etching to be optimized. It is discovered the parameters change with the size and shape of the pattern. Magnetization and structural characterization were performed by using the magneto-optical Kerr effect and a magnetic force microscope. The result shows that the nano-magnets become magnetically harder than the reference sample. The study further reveals structural details for further improvements in implanted regions.

Opponent: Stivan Sabir

Cette thèse présente le développement de tests immunologiques innovants, rapides et sensibles combinant des nanoparticules superparamagnétiques (SPN) fonctionnalisées et des micro-aimants : nos immuno-essais magnétiques exploitent les forts gradients de champ magnétique de ces micro-aimants pour capturer les complexes immunologiques liés aux SPN. L’attraction magnétique est souvent utilisée en biotechnologies car elle peut générér des forces capables de capturer des molécules d’intérêt. Les immuno-essais sur billes utilisent habituellement des aimants centi- et millimétriques pour capturer des micro-particules. Réduire la taille des particules magnétiques est très intéressant pour réduire les cinétiques de réactions, tout en diminuant les phénomènes de sédimentation et d’agrégation. Cette réduction d’échelle des particules permet aussi d’augmenter la surface de réaction et ainsi d’augmenter la sensibilité des tests. Cependant les aimants millimétriques génèrent des gradients faibles qui capturent difficilement les SPN, trop mobiles. Les micro-aimants de l’Institut Néel génèrent des forts gradients locaux et ainsi des forces magnétiques importantes. Ces technologies innovantes sont utilisées dans cette thèse pour développer des immuno-essais rapides tirant profit de la réduction d’échelle des particules et des aimants, par rapport aux technologies commerciales.Dans un premier temps, nous avons développé un test immunologique magnétique (MagIA) colorimétrique, comme approche innovante du test ELISA. Nous avons réalisé une preuve de concept pour la détection d’anticorps dirigé contre l’ovalbumine et comparé les résultats avec ceux de tests ELISA. Le test MagIA optimisé présente une limite de détection et une zone dynamique similaires au test ELISA développé avec les mêmes réactifs biologiques. Les micro-aimants fabriqués selon la méthode de micro-magnetic imprinting sont intégrés à bas coût dans les micro-puits des plaques multi-puits ELISA, et permettent la capture efficace des complexes immunologiques couplés aux SPN. La méthode est générique est permet de réaliser des tests ELISA en 30 minutes avec le même équipement.Nous avons ensuite développé un test magnétique immunologique avec une détection fluorescente locale tirant profit des propriétés de capture locale des SPN sur les micro-aimants. Ce test permet la quantification de la molécule d’intérêt en à peine 15 minutes sans étape de lavage. Une preuve de concept réalisée sur la détection de l’anticorps anti-ovalbumine a été réalisée, avec des anticorps de détection fluorescents et des micro-aimants fabriqués selon la méthode de thermo-magnetic patterning. La mesure différentielle entre le signal fluorescent provenant des complexes immunologiques couplés aux SPN localisées sur les micro-aimants, et le signal non spécifique (à l’extérieur des micro-aimants) permet la quantification d’une molécule. Ce test MLFIA (magnetically localized FIA) possède des performances jusqu’à 100 fois meilleures que les tests ELISA standard, pour la détection d’anticorps anti-ovalbumine en PBS. Le test MLFIA a ensuite été transféré à la détection de paramètres cliniques tels que la protéine C réactive, l'ostéopontine, et les sérologies de la toxoplasmose (IgG et IgM). La comparaison des résultats avec des méthodes automatisées a montré d’excellentes corrélations. Le test MLFIA présente plusieurs avantages : il est versatile, compatible avec les milieux biologiques, utilise de faibles volumes et requiert peu d’énergie. Ces résultats ouvrent la voie à une nouvelle génération de tests immunologiques sensibles et nous développons désormais un lecteur miniature pour le diagnostic portable
This thesis reports the development of innovative, sensitive and fast immunoassays combining functionalized superparamagnetic nanoparticles (SPN) and micro-magnets. Our magnetic immunoassays exploit high gradients generated by micro-magnets to capture immune-complexes captured on SPN. Magnetic attraction is widely used in biotechnology, because it provides long-range forces able to capture molecules of interest. Bead-based immunoassays use common centimetre-scale magnets to attract micro-particles. Those magnets generate low magnetic gradients and struggle to capture superparamagnetic nano-particles, which are too small and mobile to be efficiently trapped. Down-scaling the size of magnetic particles is very interesting since it allows diffusion-based transport to perform faster reactions, while avoiding particle sedimentation and aggregation. Furthermore, it increases the reaction surface, which improves the sensitivity of immunoassays. Thanks to the scaling law effects micro-magnets from Institut Néel generate high local gradients and therefore large magnetic volume forces: we use this innovative technology to develop fast immuno-assays that take advantage of a radical size reduction, compared to commercial technology.We first developed a colorimetric magnetic immunoassay (MagIA) as a new approach to standard ELISA. A proof-of-concept based on colorimetric quantification of anti-ovalbumin antibody in buffer was performed and compared with conventional ELISAs. After optimization, MagIA exhibits a limit of detection and dynamic range similar to ELISAs developed using the same biochemical tools. Micromagnets made by the micro-magnetic imprinting method can be fully integrated in multi-well plates at low cost, allowing the efficient capture of immuno-complexes carried by SPNs. The method is generic and performs magnetic ELISA in 30 min.We then developed a magnetically localized fluorescent immunoassay (MLFIA) exploiting the local capture of SPN on micro-magnets. The differential measurement of fluorescence localized on and besides micro-magnet arrays allows the detection and quantification of a molecule in only 15 minutes without fluid handling. We present a proof of concept based on the detection of monoclonal antibody anti-ovalbumin. Functionalized nanoparticles are incubated with fluorescent detection antibody and the sample containing the molecule to be detected. After a single incubation step, the nanoparticles are captured on micro-magnets made by thermo-magnetic patterning. Fluorescence is then read under a microscope. Differential measurement between the signal from the immunological complex localised on the micro-magnets and the non-specific signal localised besides micro-magnets allows the quantification of mAb anti-OVA. The performance of MLFIA was compared with conventional ELISA and exhibits a limit of detection up to 100 times better for anti-OVA mAb in PBS. For further validation, MLFIA was used to measure clinical parameters: we developed a sandwich assay to detect C-reactive protein, and a serology for Toxoplasma gondii immunoglobulin G and M or osteopontin in human samples. Comparisons with data obtained with routine clinical automatized methods show excellent correlation. Our MLFIA technology presents several key advantages: it is compatible with biological media (serum, plasma), uses small volumes and requires little energy. It also is versatile and thus can be used to detect any antigen or antibody in complex media. We are currently developing a portable prototype for point-of-care diagnostics. The results will open the way to a new generation of sensitive immunological lab-on-chip

2013/2014
Traditional semiconductor technology will reach a size limit within the next few years. A possible solution could be the use of organic molecules in technological applications as single functional units in metal-organic based devices; the success of this approach strongly depends on the understanding of the behaviour of these molecules on metallic surfaces. The interaction with metallic substrates and the interaction between the molecules themselves determine the electronic and magnetic properties of the system, and it is thus of fundamental interest to study these metal-organic interfaces both in the case of single molecules and layer structures. In this thesis, an extensive study of the electronic and magnetic properties of tetra-phenyl-porphyrin (2H-TPP) molecules adsorbed on metal surfaces is reported. By means of scanning tunnelling microscopy (STM) we studied the adsorption geometry of these molecules on the Au(111), Ag(111) and Cu(100) surfaces. By using X-ray photoemission spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, a temperature-induced conformational adaptation reaction of the 2H-TPP molecules adsorbed on the Au(111) and Ag(111) surfaces, upon annealing at 550 K, is described. A possible dehydrogenation reaction, with the formation of new C-C bonds, could explain the rotation of the molecule phenyl rings parallel to the surface plane and the associated increasing in the molecule-substrate interaction. In-situ metalation of porphyrins in ultra-high vacuum is obtained by two methods: in the first one, the metalation of 2H-TPP on Ag(111) is achieved by direct metal evaporation (Mn, Rh and Fe) on the molecular layer; in the second case we report the self-metalation of 2H-TPP through the coordination with a metal atom from the Fe(110) and Al(111) substrates. In addition, we investigated the effects of metalation and temperature-induced conformational adaptation on the molecule-substrate interaction, by means of XPS and NEXAFS, in the case of CoTPP on Ag(111). The magnetic properties resulting from the metal coordination are studied by X-ray magnetic circular dichroism (XMCD). Here, a description of the magnetic coupling of a MnTPPCl single layer with a Fe(110) ferromagnetic substrate is disclosed. Moreover, we focused on the study of the magnetic properties and exchange coupling of two layer of molecule and a ferromagnetic thin film. In the case of a MnTPP layer on FeTPP/Fe(110) the magnetic coupling extends to the second layer of molecules, for which the magnetization is opposite with respect to the substrate.
Le tradizionali tecnologie utilizzate nell’industria dei semiconduttori raggiungeranno, entro breve tempo, il limite nella miniaturizzazione dei loro componenti. Una possibile alternativa potrebbe venire dall’utilizzo di molecole organiche come singole unità funzionali in dispositivi metallo-organici; d’altra parte il successo di questo approccio dipende in maniera sostanziale dalla comprensione del comportamento di queste molecole sulle superfici dei metalli. L’interazione con il substrato metallico e la stessa interazione tra le molecole determinano le proprietà elettroniche e magnetiche di questi sistemi, ed è dunque di fondamentale interesse lo studio di queste interfacce metallo-organiche sia nel caso di singole molecole che di strutture più complesse. In questa tesi è riportato uno studio dettagliato delle proprietà elettroniche e magnetiche di tetra-fenil-porfirine (2H-TPP) adsorbite su superfici metalliche. Attraverso la microscopia a scansione a effetto tunnel (STM) è stata studiata la geometria di adsorbimento di queste molecole sulle superfici Au(111), Ag(111) e Cu(100). Utilizzando le spettroscopie XPS (X-ray photoemission spectroscopy) e NEXAFS (near-edge X-ray absorption fine structure) è descritta la reazione di adattamento conformazionale delle 2H-TPP adsorbite sulle superfici Au(111) e Ag(111) a seguito del processo di annealing a 550 K. Una possibile reazione di de-idrogenazione, con la formazione di nuovi legami C-C, può spiegare la rotazione dei gruppi fenili della molecola verso la superficie e l’aumento dell’interazione molecola-substrato ad esso associato. La metallazione in-situ delle porfirine in ultra-alto vuoto è ottenuta in due modi: nel primo, la metallazione delle 2H-TPP su Ag(111) è raggiunta con la diretta evaporazione del metallo (Mn, Rh e Fe) sullo strato di molecole; nel secondo caso, sulle superfici Fe(110) e Al(111) la metallazione avviene automaticamente tramite la coordinazione della 2H-TPP con un atomo della superficie. Inoltre, gli effetti della metallazione e dell’adattamento conformazionale sull’interazione molecola-substrato sono stati studiati, tramite XPS e NEXAFS, nel caso di CoTPP su Ag(111). Le proprietà magnetiche risultanti dalla coordinazione della molecola con un atomo metallico sono state studiate per mezzo della tecnica XMCD (X-ray magnetic circular dichroism). In particolare, viene descritto l’accoppiamento magnetico di un singolo strato di MnTPPCl con un substrato ferromagnetico Fe(110). Inoltre, ci si è focalizzati sullo studio delle proprietà magnetiche tra due strati di molecole e un film sottile ferromagnetico. Nel caso specifico di MnTPP su FeTPP/Fe(110) l’accoppiamento magnetico si estende al secondo strato di molecole, per il quale la magnetizzazione è opposta rispetto al substrato.
XXVII Ciclo
1986

Magnetization dynamics in nano-contact spin torque oscillators (STOs) is investigated from an experimental and theoretical point of view. The fundamentals of magnetization dynamics due to spin transfer torque are given. A custom-made high frequency (up to 46 GHz) in large magnetic fields (up to 2.2 T) microwave characterization setup has been built for the purpose and described in this thesis. A unique feature of this setup is the capability of applying magnetic fields at any direction θe out of the sample plane, and with high precision. This is particularly important, because the (average) out-of-plane angle of the STO free magnetic layer has fundamental impact on spin wave generation and STO operation. By observing the spin wave spectral emission as a function of θe, we find that at angles θe below a certain critical angle θcr, two distinct spin wave modes can be excited: a propagating mode, and a localized mode of solitonic character (so called spin wave bullet). The experimental frequency, current threshold and frequency tuneability with current of the two modes can be described qualitatively by analytical models and quantitatively by numerical simulations. We are also able to understand the importance, so far underestimated, of the Oersted field in the dynamics of nano-contact STOs. In particular, we show that the Oersted field strongly affects the current tuneability of the propagating mode at subcritical angles, and it is also the fundamental cause of the mode hopping observed in the time-domain. This mode hopping has been observed both experimentally using a state-of-the-art real-time oscilloscope and corroborated by micromagnetic simulations. Micromagnetic simulations also reveal details of the spatial distribution of the spin wave excitations. By investigating the emitted power as a function of θe, we observed two characteristic behaviors for the two spin wave modes: a monotonic increase of the power for increasing out-of-plane angles in the case of the propagating mode; an increase towards a maximum power followed by a drop of it at the critical angle for the localized mode. Both behaviors are reproduced by micromagnetic simulations. The agreement with the simulations offers also a way to better understand the precession dynamics, since the emitted power is strongly connected to the angular variation of the giant magnetoresistance signal. We also find that the injection locking of spin wave modes with a microwave source has a strong dependence on θe, and reaches a maximum locking strength at perpendicular angles. We are able to describe these results in the theoretical framework of non-linear spin wave dynamics.
QC 20101130

Orientador: Varlei Rodrigues
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
Made available in DSpace on 2018-08-23T00:51:37Z (GMT). No. of bitstreams: 1 Sa_ArturDominguesTavaresde_D.pdf: 7427611 bytes, checksum: 5f7375c13b84237cc30bec5c926f2f65 (MD5) Previous issue date: 2013
Resumo: Clusters, i.e. nanopartículas formadas por alguns átomos ou até 107, atraem grande interesse devido 'as propriedades peculiares que apresentam, como momento magnético aumentado, atividade catalítica, fluorescência dependente de tamanho e estruturas geométricas diferenciadas em relação ao material massivo. Isso acontece principalmente devido aos efeitos decorrentes da grande razão entre o número de átomos na superfície e o número de átomos no volume, e também por conta dos níveis discretos de energia devidos ao pequeno número de átomos presente nas estruturas. Entretanto, para que seja possível uma melhor compreensão dos mecanismos envolvidos em amostras compostas por clusters, 'e imprescindível que tenhamos um grande controle dos parâmetros cruciais como tamanho das partículas, concentração e energia de deposição. Para isso, desenvolvemos e construímos uma fonte para a produção de agregados com um número controlável de átomos, com a intenção de produzir partículas com 2 até 100 átomos. Um feixe de partículas 'e produzido, caracterizado e depositado em condições de ultra alto vácuo (UHV), utilizando-se uma fonte de clusters com magnéton sputtering. A fonte 'e baseada na proposta por Haberland et al. (1) com a inovadora introdução de um sputtering com geometria cilíndrica, com a intenção de aumentar a eficiência na criação de partículas bem como facilitar a produção de agregados de ligas. Uma fonte de clusters geralmente é constituída essencialmente de: uma fonte de átomos e uma câmara de agregação, para gerar as partículas; um sistema de lentes eletrostáticas, para guiar e focalizar o feixe; e um analisador de massa, podendo esse selecionar, ou não, as partículas em massa. Para fonte de átomos desenvolvemos dois magnéton sputterings, um magnéton circular plano típico de 1" e um magnéton cilíndrico para a erosão axial de fios metálicos. A câmara de agregação tem um comprimento variável (0-300 mm), para que possamos controlar o tamanho médio dos nano-agregados. Um skimmer, três lentes Einzel e uma Bessel-Box são utilizadas para guiar e focalizar o feixe de partículas ao longo do instrumento. Como analisador de massa, construímos um espectrômetro de massa por tempo de voo. É importante frisar que optamos por desenvolver a maioria dos componentes na própria Unicamp, estes componentes serão descritos no corpo dessa tese. O equipamento que se encontra operacional, já se mostrou capaz de produzir partículas com mais de 500 átomos, superando assim nossas expectativas iniciais. Apresentamos também a caracterização magnética de nanoestruturas granulares com nano-agregados de cobalto com 2,3 nm de diâmetro embebidos em matrizes de cobre com diferentes concentrações. A comparação dos resultados utilizando-se o triple fit e medidas de transporte mostra que apenas para baixa concentração (0,5 at.% Co) todos os experimentos são consistentes com a suposição de que as partículas são não-interagentes e a descrição teórica comumente utilizada é apropriada. Aumentando-se a concentração para 2,5 at.% e 5 at.% implica em desvios entre magnetometria e magneto-transporte
Abstract: Clusters, i.e. nano-particles formed by a few tens or up to 107 atoms, attract great interest due to their peculiar properties as enhanced magnetic moment and catalytic activity, size-specific fluorescence and non-bulky geometrical structures. This happens mainly due to effects arising from their high surface-to-bulk ratio and because of the discrete energy levels due to the small amount of atoms at these structures. However, in order to get a deeper understanding of the mechanisms taking place in cluster-assembled samples, it is fundamental to have a good control of crucial parameters such as clusters size, composition, concentration and deposition energy. In this way, we have developed and constructed a source to produce clusters with a controllable number of atoms intended to produce particles ranging from 2 up to 100 atoms. A beam of cluster ions is produced, characterized and deposited under ultra high vacuum (UHV) conditions, using a magnetron sputtering cluster source. This source is based on the design of Haberland et al. (1) with the innovative introduction of a cylindrical sputtering geometry that intends to increase the particle generation efficiency also to facilitate the production of alloy clusters. A usual clusters source is constituted essentially of an atom source and aggregation chamber, to generate the particles; electrostatic lenses, to guide them; and a mass analyzer, which may, or not, select the particles by mass. For the atom source we have designed two sputtering-like sources, a home-made 1" typical planar magnetron and also a home-made cylindrical one, for axial erosion of wire targets. The aggregation chamber has a variable length ( 0-300 mm), so we can control the average size of the clusters. A skimmer, three Einzel lenses and a Bessel-Box are used to guide charged cluster through the instrument. As mass analyzer we have built Time-Of-Flight mass spectrometer. It is important to say that we choose to build almost all the components at Unicamp, these components will be described in the body of this thesis. The equipment, which is operational, showed itself capable to produce particles with more than 500 atoms, exceeding our initial expectations. We also report on magnetic characterization of clusterassembled nanostructures with cobalt clusters with 2.3 nm diameter embedded in copper matrices at different concentrations. Results from the triple fit and transport measurements were compared and showed that only at low concentration (0.5 at % Co) all experiments are consistent with the non-interacting particles assumption and the common theoretical description is appropriate. Increasing the concentration to 2.5 at.% and 5 at.% implies deviations between magnetometry and magnetotransport
Doutorado
Física
Doutor em Ciências

Cette thèse a pour objet l’optimisation de la croissance par épitaxie par jets moléculaires dans le régime de van der Waals de couches semi-conductrices bidimensionnelles (2D) de diséléniures de métaux de transition (MoSe2, WSe2) pour les études magnéto-optiques et électriques. Cette optimisation passe par l’amélioration de la qualité cristallographique des couches sur de grandes surfaces en ajustant les paramètres de croissances (température et flux). En particulier, la maîtrise de l’état de surface du substrat est déterminante sur les mécanismes de croissance de ces couches. L’élaboration de ces matériaux de basse dimensionnalité a nécessité l’utilisation de techniques de caractérisation avancées (Diffraction de rayons X en incidence rasante, Microscopie électronique en transmission en mode haute résolution, ect). Dans cette thèse, nous nous sommes concentrés sur deux substrats particuliers : l’oxyde de silicium et le mica. Ils présentent tous les deux la particularité d’être isolants et inertes d’un point de vue électronique, ce qui est indispensable pour sonder les propriétés optiques et électriques intrinsèques des couches 2D. Finalement, nous avons développé les dopages électrique (dopage p) pour la microélectronique et magnétique (dopage Mn) pour la valleytronique
The purpose of this thesis is to optimize growth by molecular beam epitaxy in the van der Waals regime of two-dimensional (2D) semiconductor layers of transition metal diselenides (MoSe2, WSe2) for magneto-optical and electric studies. This optimization involves improving the crystallographic quality of the layers over large areas by adjusting the growth parameters (temperature and flux). In particular, the control of the surface state of the substrate is decisive on the growth mechanisms of these layers. The development of these low-dimensional materials required the use of advanced characterization techniques (Grazing incidence X-ray diffraction, High Resolved Transmission Electronic Microscopy, ect). In this thesis, we focused on two specific substrates : silicon oxide and mica. They both have the particularity of being insulating and inert from an electronic point of view, which is essential to probe the optical and electrical intrinsic properties of 2D layers. Finally, we developed electrical doping (p doping) for microelectronics and magnetic (Mn doping) for valleytronics

The ability of a ferromagnet to maintain its magnetic state in the absence of an external magnetic field has made ferromagnetic materials an important subject of study in physics since the end of the 19th century. Moreover, ferromagnetic materials are the cornerstone for data storage systems such as magnetic tapes, magnetic disk drives and magnetic random access memory. The discovery of the Giant Magneto Resistance (GMR) in 1988 suggested that, since the magnetic state of the electrical conductor has an important effect upon the current flow, there may also be an inverse influence of the current upon the magnetization. In this effect, predicted in 1989 [1] by Slonczewski and called Spin Transfer Torque, angular momentum transferred by a spin polarized current can exert a torque on the magnetization of a ferromagnetic material, changing the local magnetization and stimulating the precession of the magnetic moments, generating microwave signals. This provides a new method of manipulating magnetization without applying an external field. Large polarized currents lead to spin transfer effects which are the driving force for the magnetic dynamics of devices known as Spin Transfer Oscillators (STO). In this new kind of nano-device the emission of microwaves is stimulated by a DC electrical current and measured as a change in the output voltage due the GMR effect. The specific characteristics of these devices such as working frequency and DC current ranges, microwave emission linewidth, and maximum emission power among others, are given by the design and size of the device,and the nature of the magnetic oscillations producing the emission. Among the multiple types of STO that now exist , I have focused my research upon three of them: Spin Transfer Vortex Oscillators (STVO), Single Layer Spin Transfer Oscillators (SL-STO) and Orthogonal Pseudo Spin Valves. Within STVOs and SL-STOs we can nucleate what is called a magnetic vortex. A magnetic vortex is a curling of the in-plane of a magnetic layer with its centre pointing out of the magnetization plane. The gyration of this vortex due to STT produces a microwave emission < 1GHz with a greater emission power than that produced by the precession of magnetic moments in STOs. The phase-locked synchronisation of multiple vortices is expected to exhibit enhanced microwaved power and phase stability compared to a single vortex device, providing a solution to the drawbacks of the STO in the low frequency regime. On the other hand, Orthogonal Pseudo Spin Valves promote the nucleation of magnetic dissipative solitons, also called magnetic droplets. This type of magnetic structure has an opposite out of plane magnetization to the layer that contains it. Compared to the microwave emission of magnetic vortices , magnetic droplets have a higher frequency range and emission power. However, their nucleation is subject to large external fields being applied to the sample. In this thesis, I electrically characterized these devices and applied magnetic imaging techniques in order to go further in the understanding of the spatial features and dynamic behaviour of these magnetic structures. It is not possible to acquire this knowledge by only using electrical characterization. Understanding the magnetization dynamics in these devices is crucial for the design of STO based devices while imaging studies are required to prove the existence of these magnetic structures, as in case of the magnetic droplet. In chapter 2 I will introduce the background concepts of magnetism that are relevant to this thesis. I will go from the basics principles of ferromagnetism, its quantum mechanical treatment, and the theory that explain the dynamics of the magnetisation. I will also present the state of the art in experimental research in the field of spin transfer oscillators. My aim is to give the basic background needed to understand the results presented in this thesis. In chapter 3 I will introduce the two main experimental techniques used for imaging the magnetisation of the devices presented: Holography with Extended Reference by Autocorrelation Linear Differential Operator (HERALDO) and Time Resolved Scanning Kerr Microscopy (TRSKM). I will revise the theoretical background concepts and the development of the techniques in order to demostrate the uniqueness of each technique and how they were used in this thesis. It is interesting to note that while MOKE is a well-known and widely-used technique, far fewer laboratories in the world area able to perform time resolved measurements using MOKE, with the University of Exeter being one of them. Furthermore, HERALDO is a novel technique that is used for the first time to image magnetic structures within multilayer systems in this thesis, which is a milestone in the development of the techinque. In chapter 4 I present an investigation of the magnetization dynamics of a SL-STO. Electrical transport measurements provided an initial characterization of the device. We then used HERALDO for the first time to investigate the magnetization dynamics in an intermediate layer of a multilayer stack. We present time averaged measurements of the magnetisation of a magnetic vortex formed underneath a nano contact (NC) positioned on top of the multilayer, using a combination of x-ray holography and x-ray magnetic circular dichroism. In chapter 5 I present the first direct measurement at the time of a magnetic dissipative droplet, using holography with extended reference autocorrelation by linear differential operator (HERALDO). I studied the out of plane magnetisation of the free layer under a NC within an orthogonal pseudo spin salve. In chapter 6 I present and study STVO devices with pairs of NCs of 100 nm diameter and centre-to-centre separation D = 200 to 1100 nm, by a combination of electrical measurements and time-resolved scanning Kerr microscopy (TRSKM). It will be shown that the dynamic behaviour of vortices and anti vortices changes when the distances between the NCs within the devices is changed.

Scanning Tunnelling Microscopy (STM) is the fastest possible method of imaging the molecular orbitals of the C[subscript]60 anions with resolution at the single atom level. For the particular anions of fullerene C[subscript]60, the splitting of the molecular orbitals due to the internal Jahn-Teller effects (JT) add further difficulties in understanding the published experimental images. In the current work, the effect of JT interaction on STM recorded images is studied. For higher charged states, the Coulomb interaction affects the distribution of electrons around the ion, and then as a consequence, the STM current. The external interaction between the molecule and the surface substrate is equally important. Symmetry analysis using group theory and Hückel molecular orbital (HMO) theory are applied in order to describe the influence of the surface interactions on JT minima associated with D[subscript]3d, D[subscript]5d, D[subscript]2h, and C[subscript]2h symmetries. It represents some fullerene anions, which are adsorbed to the surface with different orientations, such as pentagon, hexagon, and double-bond prone toward the surface. Several ions with higher charges are investigated, such as C2−60, C3−60, and C4−60. In case of high symmetry orientations, the JT minima of the ions on a surface are split into subgroups with equal energies, depending on the type of orientation. The interpretation of the experimental observations is always possible for any orientation from the JT minima distribution and the contribution to the images from different components of the degenerate molecular orbitals.

Les nano-Oscillateurs à transfert de spin (STNOs) sont des dispositifs capables d'émettre une onde hyperfréquence lorsqu'ils sont pompés par un courant polarisé grâce au couple de transfert de spin. Bien qu'ils offrent de nombreux avantages (agilité spectrale, intégrabilité, etc.) pour les applications, leur puissance d'émission et leur pureté spectrale sont en général faibles. Une stratégie pour améliorer ces propriétés est de synchroniser plusieurs oscillateurs entre eux. Une première étape est de comprendre la synchronisation d'un STNO unique à une source externe. Pour cela, nous avons étudié une vanne de spin Cu60|NiFe15|Cu10|NiFe4| Au25 (épaisseurs en nm) de section circulaire de 200 nm. Dans l'état saturé perpendiculaire (champ appliqué > 0.8 T), nous avons déterminé la nature du mode qui auto-Oscille et son couplage à une source externe grâce à un microscope de force par résonance magnétique (MRFM). Seul un champ micro-Onde uniforme permet de synchroniser le mode oscillant de la couche fine car il possède la bonne symétrie spatiale, au contraire du courant micro-Onde traversant l'échantillon. Ce même échantillon a ensuite été étudié sous faible champ perpendiculaire, les deux couches magnétiques étant alors dans l'état vortex. Dans ce cas, il est possible d'exciter un mode de grande cohérence (F/ ∆F >15000) avec une largeur de raie inférieure à 100 kHz. En analysant le contenu harmonique du spectre, nous avons déterminé que le couplage non-Linéaire amplitude-Phase du mode excité est quasi nul, ce qui explique la grande pureté spectrale observée, et qu'en parallèle, la fréquence d'oscillation reste ajustable sur une grande gamme grâce au champ d'Oersted créé par le courant injecté. De plus, la synchronisation de ce mode à une source de champ micro-Onde est très robuste, la largeur de raie mesurée diminuant de plus de cinq ordres de grandeur par rapport au régime autonome. Nous concluons de cette étude que le couplage magnéto-Dipolaire entre STNOs à base de vortex est très prometteur pour obtenir une synchronisation mutuelle, le champ dipolaire rayonné par un STNO sur ses voisins jouant alors le rôle de la source micro-Onde. Nous sommes donc passés à l'étape suivante, à savoir la mesure expérimentale de deux STNOs similaires séparés latéralement de 100 nm. En jouant sur les différentes configurations de polarités des vortex, nous avons réussi à observer la synchronisation mutuelle de ces deux oscillateurs
Spin transfer nano-Oscillators (STNOs) are nanoscale devices capable of generating high frequency microwave signals through spin momentum transfer. Although they offer decisive advantages compared to existing technology (spectral agility, integrability, etc.), their emitted power and spectral purity are quite poor. In view of their applications, a promising strategy to improve the coherence and increase the emitted microwave power of these devices is to mutually synchronize several of them. A first step is to understand the synchronization of a single STNO to an external source. For this, we have studied a circular nanopillar of diameter 200~nm patterned from a Cu60|Py15|Cu10|Py4|Au25 stack, where thicknesses are in nm. In the saturated state (bias magnetic field > 0.8 T), we have identified the auto-Oscillating mode and its coupling to an external source by using a magnetic resonance force microscope (MRFM). Only the uniform microwave field applied perpendicularly to the bias field is efficient to synchronize the STNO because it shares the spatial symmetry of the auto-Oscillation mode, in contrast to the microwave current passing through the device. The same sample was then studied under low perpendicular magnetic field, with the two magnetic layers in the vortex state. In this case, it is possible to excite a highly coherent mode (F/∆F>15000) with a linewidth below 100 kHz. By analyzing the harmonic content of the spectrum, we have determined that the non-Linear amplitude-Phase coupling of the excited mode is almost vanishing, which explains the high spectral purity observed. Moreover, the oscillation frequency can still be widely tuned thanks to the Oersted field created by the dc current. We have also shown that the synchronization of this mode to a microwave field source is very robust, the generation linewidth decreasing by more than five orders of magnitude compared to the autonomous regime. From these findings we conclude that the magneto-Dipolar interaction is promising to achieve mutual coupling of vortex based STNOs, the dipolar field from a neighboring oscillator playing the role of the microwave source. We have thus experimentally measured a system composed of two STNOs laterally separated by 100 nm. By varying the different configurations of vortex polarities, we have observed the mutual synchronization of these two oscillators

Les nano-oscillateurs spintroniques présentent des propriétés remarquables en termes de détection radiofréquence. Leurs tailles nanométriques, leur fonctionnement à température ambiante et leurs compatibilité CMOS en font des candidats sérieux pour apporter la fonction d’analyse spectrale instantanée dans des systèmes embarqués. Les travaux de cette thèse portent sur les propriétés de détection des STNOs à base de vortex magnétiques. Un des effets conférant aux STNOs la possibilité de détecter un signal rf est l’effet diode de spin. Une source rf permet de créer le signal à détecter. Lorsque la fréquence du courant rf injecté dans le STNO correspond à sa fréquence de résonance, une tension de rectification est créée à ses bornes. La mesure de cette tension par un simple voltmètre permet alors de déterminer la présence d’un courant rf. L’étude de l’évolution de la fréquence de résonance en fonction du rayon du STNO, du courant dc et du champ magnétique a mis en avant la possibilité de choisir la fréquence de résonance et de l’accorder avec ces paramètres. Dans une perspective applicative, cette propriété est essentielle pour allouer un STNO à une fréquence spécifique à détecter. De plus, la taille nanométrique des STNOs permettent d’envisager un système composé d’un réseau de milliers, voire de millions de STNOs contenues sur une puce fonctionnant à température ambiante. Cependant plusieurs problématiques se posent. La sensibilité du STNOs à un signal rf extérieur doit permettre de déterminer l’état d’occupation d’un canal de fréquence par une simple mesure de la tension ou par un comparateur de tension. Cela nécessite une variation de tension de l’ordre de la dizaine de mV. L’effet diode de spin ne permettant pas d’atteindre de telle variation, un autre effet, mesuré pour la première fois à l’Unité Mixte de Physique CNRS/Thales, appelé expulsion de vortex magnétique, est étudié. Ce phénomène a lieu quand le cœur de vortex franchit les bords du STNO lors de sa dynamique induite par transfert de spin. Grâce à cet effet, l’amplitude de la variation de tension peut atteindre jusqu’à 25 mV dans les STNOs caractérisés dans le cadre de nos travaux. De plus, ce phénomène est également accordable en fréquence. Dans une perspective applicative, un réseau de STNO doit être crée afin d’allouer un STNO à une gamme de fréquence spécifique et ainsi couvrir une large bande de fréquence. La répartition du courant rf vers tous les STNOs est donc une problématique à laquelle nous avons apporté une solution. L’excitation du cœur de vortex par un champ rf nous permet en effet d’exciter un grand nombre de STNO grâce à une ligne inductive lithographiée au-dessus des STNOs. La possibilité d’expulser le cœur de vortex, dans ces conditions, a été démontré. Nous avons alors étudié la dynamique du cœur de vortex induite par un champ rf lors de l’expulsion. Ces études temporelles et fréquentielles nous ont non seulement apporté des informations sur le temps de détection d’un signal rf par le STNO mais aussi sur son aimantation dans le régime d’expulsion. De plus, l’accord en fréquence du STNO est possible même lors de l’excitation du cœur de vortex par un champ rf. Enfin, ces études nous ont permis de mettre en place, étape après étape une preuve de concept démontrant la faisabilité de la détection rf avec des nano-oscillateurs spintronique. Les différentes études du phénomène d’expulsion du cœur de vortex alliées à un travail technique de conception et de fabrication considérable a permis de converger vers une solution qui constitue un point de départ vers le développement d’un détecteur d’occupation de spectre spintronique large bande, tenant sur une puce et fonctionnant à température ambiante
Spintronic nano-oscillators have remarkable properties in terms of radio frequency detection. Their nanoscale sizes, room temperature operation, and CMOS compatibility make them serious candidates for providing instantaneous spectral analysis in embedded systems. This thesis concerns the detection properties of magnetic vortex-based STNOs. One of the effects conferring on STNOs the possibility of detecting a rf signal is the spin diode effect. An rf source is used to create the signal to be detected. When the rf current frequency injected into the STNO corresponds to its resonant frequency, a rectification voltage is created at its terminals. The measurement of this voltage by a simple voltmeter makes possible to determine the rf current presence. The evolution study of the resonance frequency as a function of the STNO radius, the dc current and the magnetic field has highlighted the possibility of choosing the resonant frequency and tuning it with these parameters. From an application point of view, this property is essential for allocating an STNO to a specific frequency to be detected. Furthermore, the STNO nanometric allows us to envisage a network of thousands, even millions of STNOs contained on a chip operating at ambient temperature. However, several problems arise. The STNO sensitivity to an external rf signal must allow to determine the occupancy state of a frequency channel by a simple measurement of the voltage or with a voltage comparator. This requires a voltage variation of ten mV order. The spin diode effect doesn’t allow to achieve such variation. Another effect, measured for the first time at the Unité Mixte de Physique CNRS/Thales, called magnetic vortex expulsion, is studied. This phenomenon occurs when the vortex core crosses the STNO edges during its spin transfer induced dynamics. Thanks to this effect, the voltage amplitude variation can reach up to 25 mV in the STNOs characterized during this thesis. Moreover, this phenomenon can be tuned. From an application perspective, a network of STNOs must be created in order to allocate an STNO to a specific frequency range and thus cover a broad frequency band.The rf current distribution to all STNOs is therefore a problem to which we have brought a solution. The excitation of the vortex core by a rf field allows us to excite a large number of STNO thanks to an inductive line lithographed above the STNOs. The possibility of expelling the vortex core under these conditions has been demonstrated. We then studied the vortex core dynamics induced by an rf field during the expulsion. A time and frequency domain studies not only provided us detection time information of an rf signal by the STNO but also on its magnetization in the expulsion regime. Moreover, the STNO frequency tuning is possible even when the vortex core is excited by an rf field. Finally, these studies enabled us to implement step by step a proof of concept demonstrating the rf detection feasibility with spintronic nano-oscillators. The various studies of vortex core expulsion combined with a considerable technical work of design and manufacture finally allowed us to converge towards a solution that constitutes a starting point towards the development of a broadband spintronic spectrum occupancy detector, contained on a chip and operating at room temperature

Les commutables moléculaires sont des molécules qui peuvent moduler leurs propriétés (physiques, chimiques) sous l'influence d'un stimulus externe). Les remarquables propriétés des objets ont suscité un vif intérêt dans l'électronique moléculaire, et plus généralement, dans le domaine des matériaux multifonctionnels. Ce projet de thèse s'est inscrit dans le cadre d'une première collaboration entre les équipes ERMMES et Polymères de l'Institut Parisien de Chimie Moléculaire (IPCM). L' objectif a consisté à développer des voies de synthèses générales de (nano)matériaux hybrides à partir de commutables moléculaires magnétiques. Ce travail s'est essentiellement appuyé sur l'utilisation de complexes à transition de spin ainsi que sur une famille de composés cyanurés Fe/Co photomagnétiques. Ces systèmes ont été fonctionnalisés à leur périphérie, sur les ligands "scorpionates" de type tris(pyrazolyl)borate utilisés pour leur préparation. L'influence du groupement fonctionnel sur les propriétés des différents commutables a ensuite été étudiée, afin de déterminer les meilleurs candidats pour la conception des matériaux hybrides. Finalement, la déposition ou l'intégration des commutables magnétiques fonctionnalisés sur surfaces ou dans des polymères organiques respectivement, a été approchée par différentes méthodes en solution. Ce manuscrit reprend ainsi l'ensemble de ces études
Molecular switchesare molecules that can asdjust their(chemical, physical) properties in response to an external stimulus. The fascinating properties of molecular switches have drawn most attention in molecular electronics and more generally in advances materials research. This PhD project was developped at the frontiers of ERMMES and Polymeres research themes, in the framework of a first collaboration. Our major interest was to establish reliable synthetic routes for the design of hybrid (nano)materials based on magnetic molecular switches. The work was particularly focused on spin crossover complexes and a family of photomagnetic cyanide-bridged Fe/Co cages. These switches were first functionalized at their periphery, on the tris(pyrazolyl)borate capping ligand used for their synthesis. The functionalization influence on the switches properties were carried out to target the best candidates for hybrid materials design. Then, we dedicated efforts on the intergration of magnetic molecular switches into two main classes of materials, (i) surfaces and (ii) organic polymers, through wet-chemistry approaches. This manuscript combines this set of studies

Dans la première partie de ce travail de thèse, nous nous sommes intéressé à l’étude de l’anisotropie magnétique au sein de complexes mononucléaires de Ni(II) et de Co(II) pentacoordinés de géométrie allant de la pyramide à base carrée jusqu’à la bipyramide trigonale. Pour les complexes mononucléaires, nous avons montré que pour une géométrie donnée, la nature de l’ion métallique a une influence importante sur l’anisotropie magnétique.Nous avons étudié l’effet de la géométrie pour un même ion métallique. Dans le cas d’une géométrie bipyramidale trigonale (symétrie C3v), nous avons montré que le complexe de Co(II) possède un axe facile de l’aimantation et donc un blocage de l’aimantation qui conduisent à l’ouverture d’un cycle d’hystérèse à basse température. Ce type de complexe peut donc être utilisé pour le stockage de l’information. Dans la deuxième partie du travail, nous avons étudié les propriétés magnétiques de complexes binucléaires. Un complexe binucléaire de Co(II) pontés par deux Cl- présente un faible couplage ferromagnétique et un blocage de l’aimantation.Enfin, l’autre aspect de ce travail est de réaliser une molécule binucléaire où deux ions anisotropes, chacun possédant un axe facile de l’aimantation, soient faiblement couplés de manière antiferromagnétique. Pour ce faire, nous avons étudié des composés avec des ligands de type cryptant où la géométrie autour des Co(II) est bipyramide trigonale. Nous avons trouvé qu’avec un ligand pontant de type Cl- ou Br-, l’interaction d’échange est beaucoup plus importante que l’anisotropie locale des ions Co(II) conduisant à un comportement magnétique où les ions perdent leur caractère local. Ce travail ouvre la perspective de synthétiser le même type de complexes mais avec des ponts de plus grande taille pour diminuer l’intensité du couplage antiferromagnétique
In the first part of this thesis, we studied the magnetic anisotropy of pentacoordinated mononuclear Ni(II) and Co(II) complexes possessing geometries from square pyramid to trigonal bipyramid. We have shown that, for a given geometry, the metal ion nature has an important influence on the magnetic anisotropy.Then, we studied for a given metal ion the effect of geometry on its magnetic anisotropy. In the case of a trigonal bipyramidal geometry (C3v symmetry), we showed that Co(II) has an Ising type anisotropy (easy axis of magnetization) and thus a blocking of magnetization that leads to an opening of a hysteresis cycle at low temperature. This type of complexes can be used for storing data albeit at low temperature.In the second part of the work, we studied the magnetic properties of binuclear complexes. A binuclear Co(II) complex bridged by two Cl- has a weak ferromagnetic coupling and a blocking of its magnetization.Finally, another aspect of this work was to design binuclear complexes, where two anisotropic ions having each one an easy axis of magnetization, are weakly antiferromagnetically coupled. To do this, we have studied compounds with cryptand ligands where the geometry around the Co (II) is trigonal bipyramid. We found that with a Cl- or Br- bridging ligand, the exchange interaction is much more important than the local anisotropy of Co(II) ions leading to a magnetic behavior where the ions lose their local character. This work opens up prospects for synthesizing the same type of complex but with larger bridges to decrease the intensity of the antiferromagnetic coupling

Ni80Fe20 and Ni80Fe20/NiO films and nano-stripes were characterized magnetically through AC and DC susceptibility measurements, and hysteresis loops as a function of field and temperature. While the near-pattern films were characterized in the in-plane configuration only, the nano-stripes were characterized in parallel, transverse and the perpendicular field configurations. The effects of the constrained geometry on the coercivity, exchange bias field, and the superparamagnetic blocking temperature were studied. It was determined that the coercivity, exchange bias field and the superparamagnetic blocking temperature can be controlled, not only by using a patterned media instead of a plane film, but also by the orientation of that pattern.

碩士
國立成功大學
地球科學系
102
The objective of this study is to investigate the magnetic properties of nano-hematite, nano-magnetite, and nano-maghemite with morphologies of nano-particle, nano-rod, nano-tube, and nano-ring. Four crystal morphologies of nano-hematite are synthesized by a hydrothermal method. Nano-magnetite is prepared via nano-hematite by using carbon reduction method. Nano-maghemite is obtained by oxidation of nano-magnetite. The particle-shaped nano-hematite has a granular morphology with aparticle size of 45~85 nm; the nano-rod is 50~100 nm in width and 250~350 nm in length; nano-tube has a inner-diameter of 40~85 nm width and 150~300 nm length; nano-ring shows a inner-diameter of 20~45 nm and outer-diameter of 70~100 nm. The particle size and morphology of nano-magnetite and nano-maghemite are almost the same as nano-hematite. It exhibits that all nano-hematites have a weak ferro-magnetism with multi-domains, however, all nano-magnetites and nano-maghemites are ferri-magnetic with pseudo-single-domain measured by superconducting quantum interference device magnetometer. The spatial distribution of magnetism are characterized by magnetic force microscopy (MFM). The MFM phase images show bright and dark areas, implying ferro-magnetic domains for nano-magnetite and nano-maghemite. Moreover, it reveals a complicated magnetic arrangement for nano-magnetite and nano-maghemite with crystal shapes of rod, tube and ring. Nano-magnetite and nano-maghemite with particle-shape both have a single-domain. This suggests the crystal structure and morphology have an impact on magnetic properties. The MFM technique could be applied in the explaination of paleomagnetism and environmental implications of fault zones.

碩士
萬能科技大學
材料科學與工程研究所
101
There are two works in our research. The first one is prepare Fe3O4 Nanoparticles with superparamagnetism by using precipitation method. The effects on the characteristics of NPs by changing prepared parameters are investigated. The second one is utilize sol gel method to prepare various Fe3O4-SiO2-TiO2 Nanoparticles (F.S.T. NPs). The F.S.T. NPs were encapsulated with high stability SiO2 and photo catalyst TiO2 respectively. The effects on the characteristics of F.S.T. NPs by changing prepared parameters are also investigated. The morphologies, sizes, constructions and magnetisms of NPs and F.S.T. NPs were determined with Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), Energy Dispersive Microscopy (EDS), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Superconducting Quantum Interference Device (SQUID) respectively. The results of experiments described as following: The Fe3O4 NPs all display superparamagnetism in this task. They have the smallest particle size when prepared parameter is pH 12, 85 ℃ and 700 rpm. Its range of particle size located at 6~8nm. The Fe3O4 NPs used as the core material, to form the F.S NPs with core-shell construction via adding appropriate amount of deionized water, ethanol, catalyst and precursor. Then TiO2 encapsulates on the surface of F.S NPs. The F.S.T. NPs possess superparamagnetism and photo catalyst are prepared successfully.

碩士
義守大學
材料科學與工程學系
92
The effect of iron oxide（Fe2O3）adding into the glass-ceramics, Li2O-Fe2O3-MnO2-CaO-P2O5-SiO2（LFMCPS）, on the crystalline phase transition, microstructures, the grain size of iron oxide phases, and magnetic properties were systematically studied in this thesis. The exothermic peak in DTA measurements for the bulk sample, is about 100℃ different from that for the powder sample illustrates that a surface nucleation process is undertaken in the LFMCPS glass ceramics system. In parallel, the X-ray diffraction pattern proves that the exothermic peak can be resulted form the formation of lithium silicate. After the heat treatment at 850℃ for 4 hours, crystalline phases of LiMn2O4, β-wollastonite（β-CaSiO3）, lithium silicate（Li2SiO3）, Ca(Mn, Ca)Si2O6, and Li2Ca4Si4O13 were found in all LFMCPS glass-ceramics specimen. However, the (Li, Mn)Ferrite phase was found in the 4wt% Fe2O3 LFMCPS and the Li2FeMn3O8 phase was formed addition to the (Li, Mn)Ferrite as the content of Fe2O3 increased to 8wt%. The microstructure studied by TEM indicates that the (Li, Mn)Ferrite particles dispersed in the matrix of the β-wollastonite. The grain size of (Li, Mn)Ferrite particles smaller than 100nm with an average size of 40nm is found in the 4wt% Fe2O3 LFMCPS glass-ceramics, but the grain size distribution of the (Li, Mn)Ferrite becomes wider ranging from 1μm to 5nm. as the content of Fe2O3 increased to 8 wt%. Based on the experimental results from SQUID and ESR spectrum, the LFMCPS glass-ceramic with 4wt% Fe2O3 exhibits mixed superparamagnetic and ferromagnetic behaviors, but the glass-ceramic with 8 wt %Fe2O3 exhibits ferromagnetic behavior. The superparamagnetic behavior can be attributed to those (Li, Mn)Ferrite with grain size smaller than 40nm, but the ferromagnetic behavior can be attributed to those (Li, Mn)Ferrite of larger grain size.

博士
國立臺灣大學
機械工程學研究所
97
Micro-nano structural components are the key components to be applied in future instrumentation for digital optoelectronics, telecommunications, flat panel displays, and bio-medicine. The conventional micro-component production technology requires a rigid mold of complicated manufacturing processes, expensive precision equipment, high temperature, and high pressure cooling processes. Therefore, the process has disadvantages, such as time-consuming, costly, and limited in visualization and controllability. This study aimed to develop a micro-nano structural imprinting processing technology of low temperature, low pressure, and rapid prototyping magnetic soft mold. It first integrated the micro-electro-mechanical process, laser processing/gas micro-thermo imprinting micro-structural manufacturing process, Anodic Aluminum Oxide (AAO) method, and nano oxidation technology to produce micro-nano structural patterns. Then, it employed PDMS composite magnetic materials to create a micro-nano structural magnetic soft mold of appropriate structural strength and flexibility by casting mold, and then prepared polymer materials. In the initial stage, it discussed the imprint forming of micro structural reproduction, using gas-assisted powder imprinting micro-forming technology. Then, it employed self-developed magnetic-assisted imprinting processing technology (including electromagnetic controllable imprinting process and electromagnetic UV imprinting process) to discuss the production and detection of magnetic-assisted imprinting processes for micro-nano structural components. Finally, it developed a magnetic roller imprinting process equipment, and successfully produced magnetic rollers, while analyzing and exploring key manufacturing technologies. The main research contents included discussion on micro-nano structural mold processing technology and its applications, analysis and exploration on gas-assisted powder imprinting micro-forming technology, discussion on magnetic-assisted micro-nano structural imprinting process, discussion on micro-nano component detection analysis and development of related processing procedures, and discussion and development of magnetic-assisted roller micro imprinting processing equipment. This study successfully established the integrated technological platform of micro-electro-mechanical processing procedures, laser processing/gas micro-thermo imprinting of micro structure processing procedures, AAO method, nanooxidation processing procedures to prepare micro-nano structural molds supplemented with PDMS composite magnetic material casting imprinting film, and micro nano magnetic soft mold imprinting reproduction, according to magnetic-assisted imprinting processing procedure/magnetic roller imprinting processing procedure. This method is innovative and creative in terms of processing procedures, and has advantages of simple, fast, inexpensive, and available for mass production, as well as providing a better alternative in the reproduction of micro structural components, contributing to the upgrading of the science, and technological industry of micro nano systems.

碩士
東海大學
物理學系
93
The main purpose of this research is to study the influences of oxygen exposure on the magnetic properties of Co/Ge(111) ultrathin films in the ultra high vacuum (UHV), and this topic has been attacked using surface magneto-optic Kerr effect (SMOKE) technique for magnetic measurement and Auger electron spectroscopy (AES) for compositional analysis. No magnetic hysteresis loop on the polar configuration is found for Co/Ge(111) films with oxygen exposure. On the longitudinal configuration, the coercivity enhances drastically, but the remanence Kerr intensity reduces slightly with increasing the oxygen exposure time. Besides, no exchange bias phenomenon is observed for Co/Ge(111) films with oxygen exposure after cooling in the magnetic field of 400 Oe to 125 K. From Auger electron spectroscopy, it is found that no oxygen adsorption occurs on either Ge(111) surface or CoGe compound interfaces in ultra high vacuum environment. As the thickness of Co films increases above 6 monolayers, pure cobalt islands form on the surface and the amount of oxygen on the surface layers increases with increasing the oxygen exposure time. From the depth profiling measurements, it is shown that oxygen always distributes on the topmost layers of the film, suggesting that oxygen plays a role as a surfactant. The adsorbed oxygen influences the electronic density of states of Co and leads to the changes of the magnetic properties. The appearance of the O/Co/Ge interface could modify the stress anisotropy, resulting in an increase of the coercivity of ultrathin Co/Ge(111) film.