Diese Arbeit untersucht die vielfältigen Wechselwirkungen zwischen elektronischen und strukturellen Eigenschaften in Perovskit-Oxiden und in einem molekularen Kristall. Optische Anregung mit ultrakurzen Lichtimpulsen verändert die elektronische Struktur und die Dynamik der damit verbundenen reversiblen Gitterveränderung wird mit zeitaufgelöster Femtosekunden Röntgenbeugung direkt aufgezeichnet. Eine Nanostruktur aus metallischen und ferromagnetischen Strontium Ruthenat (SRO) und dielektrischen Strontium Titanat Schichten dient als Modellsystem, um optisch induzierten Druck auf einer subpikosekunden Zeitskala zu untersuchen. In der ferromagnetischen Phase zeigen phononischer und magnetostriktiver Druck eine vergleichbare ultraschnelle Dynamik und eine ähnliche Größe unterschiedlichen Vorzeichens. Die Amplitude des magnetischen Drucks folgt dem Quadrat der temperaturabhängigen Magnetisierung. In einem weiteren Doppelschichtsystem komprimiert der sich ultraschnell aufbauende phononische Druck in SRO benachbarte ferroelektrische Blei Zirkonat Titanat Schichten. Dies reduziert die tetragonale Verzerrung von bis zu 2 Prozent innerhalb 1.5 Pikosekunden und koppelt an die ferroelektrische "weiche Mode", beziehungsweise an die Ionenverschiebung innerhalb der Einheitszelle. Damit verbunden wird die makroskopische Polarisation bis zu 100 Prozent reduziert; aufgrund der Anharmonizität der Kopplung mit einer Verzögerung von 500 Femtosekunden. Femtosekunden Photoanregung von Chromophoren in einem molekularen Kristall induziert eine Änderung des Diopolmomentes durch intramolekularen Ladungstransfer. Die Änderung der gestreuten Röntgenintensität weist auf eine Molekül-Rotationsbewegung in der Umgebung angeregte Dipole hin, welche der 10 Pikosekunden Dynamik des Ladungstransfer folgt. Die transienten Röntgenstreusignale werden vollständig von der kollektiven Solvatation bestimmt und verdecken lokale, intramolekulare Strukturänderungen. / This thesis investigates the manifold couplings between electronic and structural properties in crystalline Perovskite oxides and a polar molecular crystal. Ultrashort optical excitation changes the electronic structure and the dynamics of the connected reversible lattice rearrangement is imaged in real time by femtosecond X-ray scattering experiments. An epitaxially grown superlattice consisting of alternating nanolayers of metallic and ferromagnetic strontium ruthenate (SRO) and dielectric strontium titanate serves as a model system to study optically generated stress. In the ferromagnetic phase, phonon-mediated and magnetostrictive stress in SRO display similar sub-picosecond dynamics, similar strengths but opposite sign and different excitation spectra. The amplitude of the magnetic component follows the temperature dependent magnetization square, whereas the strength of phononic stress is determined by the amount of deposited energy only. The ultrafast, phonon-mediated stress in SRO compresses ferroelectric nanolayers of lead zirconate titanate in a further superlattice system. This change of tetragonal distortion of the ferroelectric layer reaches up to 2 percent within 1.5 picoseconds and couples to the ferroelectric soft mode, or ion displacement within the unit cell. As a result, the macroscopic polarization is reduced by up to 100 percent with a 500 femtosecond delay that is due to final elongation time of the two anharmonically coupled modes. Femtosecond photoexcitation of organic chromophores in a molecular, polar crystal induces strong changes of the electronic dipole moment via intramolecular charge transfer. Ultrafast changes of transmitted X-ray intensity evidence an angular rotation of molecules around excited dipoles following the 10 picosecond kinetics of the charge transfer reaction. Transient X-ray scattering is governed by solvation, masking changes of the chromophore''s molecular structure.

Half-metallic ferromagnets (HMFs), with fully spin-polarized conduction electrons, are prime candidates for optimizing spintronic devices. Many Heusler compounds (a class of ternary and quaternary intermetallics) are predicted to be HMFs, in particular Co$_{2}YZ$ (where $Y$ is usually another transition metal, and $Z$ is an s-p element). Crystal structure is controlled by thermodynamics to a large extent. Ideally, one should be able to control and optimize properties which are of interest by appropriately "tuning" the structure (e.g. annealing), but first one must understand the structure and its relation to observed physical properties. A local structural probe technique such as nuclear magnetic resonance (NMR) is an essential tool for identifying and quantifying the various atomic-scale orderings. Different Heusler structure types and antisite disorders affect the material's physical properties. In this thesis, order-disorder phenomena in both bulk and thin film samples of Co$_2$Mn$_{1-x}$Si$_x$ and Co$_2$Mn$_{1-x}$Fe$_x$Si have been systematically studied using NMR. Though it is the films which are directly implemented in actual devices, studying bulk samples as model systems provides invaluable information regarding the material properties. The evolution of local atomic structure in numerous thin films has been shown to depend greatly on preparation parameters, including post-deposition annealing temperature, and specific stoichiometry. For Co$_2$MnSi films, the ideal post-annealing temperature for promoting the $L2_1$ atomic structure was found; the threshold temperature above which structure continues to become higher-ordered in the bulk, but where too much interdiffusion at the buffer interface occurs, degrading the smooth interfaces necessary for high magnetoresistance ratios. NMR also adds evidence that Co$_2$Mn$_x$Si$_{0.88}$ ($x>$1) electrodes in magnetic tunnel junctions have highest tunneling magneto-resistance because the excess Mn suppresses the formation of detrimental Co$_{Mn}$ antisites. A systematic investigation of several thermal and magnetic properties, including Sommerfeld coefficients, Debye temperatures, saturation magnetic moments, spin-wave stiffness, and magnon specific heat coefficient, were measured for selected Co$_2$-based ternary and quaternary Heusler compounds. Obtained values were compared with theoretical ones calculated using electronic band structure methods. It has been systematically shown that adding a magnon term to the specific heat has a negligible effect on the electronic contribution in all cases.

L’intégration de matériaux ferromagnétiques dans des hétérostructures semi-conductrices offre aujourd'hui de nouvelles perspectives dans le domaine de l’électronique de spin. Dans ce manuscrit sont présentés les résultats de la croissance par épitaxie par jets moléculaires d’hétérostructures de Mn5Ge3 sur Ge(111). Le Mn5Ge3 est un composé ferromagnétique jusqu'à température ambiante qui a l’avantage de pouvoir s’intégrer directement au Ge, semiconducteur du groupe IV. S'agissant d'un matériau relativement nouveau, un des efforts majeurs a porté sur la maîtrise de la croissance des couches minces de Mn5Ge3 par la technique d'épitaxie en phase solide (SPE). Un fort accent a été mis sur les caractérisations structurales, la détermination des relations d'épitaxie avec le Ge(111), afin de les relier aux propriétés magnétiques des films. La seconde partie de ce travail a été consacrée à l'étude des processus cinétiques d'incorporation de carbone dans les couches minces de Mn5Ge3. La combinaison des différents moyens de caractérisations structurales et magnétiques a permis d'aboutir à une augmentation notable de la température de Curie tout en conservant une excellente qualité structurale de la couche et de l'interface avec le Ge et une stabilité thermique jusqu’à 850°C. Tous ces résultats indiquent que les couches minces de Mn5Ge3épitaxiées sur Ge(111) apparaissent comme des candidats à fort potentiel pour l'injection de spin dans les semi-conducteurs du groupe IV / Spin-electronics based on ferromagnetic metal/semiconductor systems offer a pathway toward integration of information storage and processing in a single material. This emerging fieldaims to create a new generation of electronic devices where two degrees of freedom will be associated: spin and charge of carriers. In this context, the outcome of this thesis is toelaborate a novel ferromagnetic compound, namely Mn5Ge3, on Ge using molecular beamepitaxy method. The interests in this compound are manyfold: it can be stabilized as a uniquephase on Ge(111) in the form of epitaxial thin films, it is ferromagnetic until room temperature and it is compatible with Si-based conventional microelectronics. In this work,one major effort was devoted to the epitaxial growth of Mn5Ge3 on Ge using Solid PhaseEpitaxy method. By combining structural and magnetic characterizations, we demonstrated high quality epitaxial thin Mn5Ge3 films with good magnetic properties. We also studied theeffect carbon incorporation on the structural and magnetic properties of epitaxial Mn5Ge3films. The carbon-doped films exhibit a high Curie temperature with an atomically smoothinterface and a high thermal stability. All these results show that Mn5Ge3 is a promisingcandidate opening up the ways for spin injection via tunnel effect through the Schottky barrierinto Ge

The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between FexCo1-x and Co3-xFexOy. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing Ms=210 emu/g. Morphological control of FexCo1-x alloy was achieved by formation of linear chains using an Hext. The final study of the FexCo1-x chains used DoE to determine factors to control FexCo1-x, diameter, crystallite size and morphology. [Ag] with [Metal] provide statistically significant control of crystallite size. [OH]/[Metal] predict 100 % FexCo1-x at > 30. To conclude section 1, a morphological study was performed on synthesis of Co3-xFexOy using the polyol process. Co3-xFexOy micropillars were synthesized at various sizes. The close proximity of the particles in the nanostructure produced an optical anisotropy and was magnetically induced which is evidence for the magneto-birefringence effect. The second non-conventional synthetic approach involves continuous flow (CF) chemistry. Co nanoparticles (Ms=125 emu/g) were newly synthesized by aqueous reduction in a microreactor and had 30 ±10 nm diameter and were produced at >1g/hr, a marker of industrial-scale up viability. The final work was the CF synthesis of FexCo1-x. The FexCo1-x was synthesized with limitation to the composition. The maximum FexCo1-x phase composition at 20 % resulted from the aqueous carrier solvent triggering oxide formation over FexCo1-x.

Ce mémoire présente les travaux réalisés durant ces trois années de thèse. Ils se sont orientés autour de l'étude des propriétés électroniques et magnétiques des matériaux pour la spintronique. Ce domaine d'avenir doit encore trouver les matériaux adaptés qui permettraient de réaliser les concepts liés à la spintronique. Nos résultats sont les suivants. Nous avons proposé un nouveau modèle qui décrit l'arrangement magnétique dans les couches minces ferromagnétiques possédant une anisotropie uniaxiale. Le modèle apporte une meilleure description des largeurs de domaine en fonction de l'épaisseur ainsi qu'une bonne estimation de l'épaisseur critique à partir de laquelle les domaines de Weiss ne sont plus stables. L'ensemble d'équations en unité réduite découlant du modèle apporte quant à lui un outil supplémentaire aux expérimentateurs. L'étude ab-Initio fait sur les semi-Conducteurs magnétiques dilués à mis en évidence l'importance de la corrélation forte et de l'effet Jahn-Teller dans les matériaux tel que le (Ga,Mn)N et le (Zn,Cr)S. Ces calculs confirment l'ensemble des données expérimentales existantes sur le (Ga,Mn)N. La modélisation analytique apporte un complément aux calculs ab-Initio en faisant le lien entre les paramètres expérimentaux et la théorie de Vallin, très largement utilisée pour interpréter les mesures optiques du (Zn,Cr)S. Nos calculs ab-Initio ont montré que le métacinabre est un isolant topologique robuste, qui se distingue par la présence d'un cône de Dirac extrêmement anisotrope. Les effets de passivation à l'hydrogène influencent les états de surface des isolants topologiques de la série HgX (X : S, Se, Te). / This thesis contains the scientific work of three years. The main topic can be defined as follows : study of electronic and magnetic properties of materials for spintronics. That technology of the future has still to find the necessary materials to realize new concepts. Our results are the following : We propose a new model to describe the magnetic configuration in thin ferromagnetic film with uniaxial anisotropy. It gives a better description of domain widths in function of film thickness and permits to obtain a good evaluation of the critical thickness where domains of Weiss type are no longer stable. The set of equations in reduced units is a useful tool to analyze experimental data. The ab-Initio study of diluted magnetic semiconductors has demonstrated the combined effect of strong correlations and Jahn-Teller distortion in (Ga,Mn)N and (Zn,Cr)S. The calculations confirm the experimental results of (Ga,Mn)N. We develop an analytical model that is complementary to the ab-Initio calculations and permits to create a link between several experimental parameters, the ab-Initio calculations and the former theory of Vallin. It has been used to interpret the optical measurements of (Zn,Cr)S. Our ab-Initio studies show that metacinnabar is a strong topological insulator with one peculiarity, it has a highly anisotropic Dirac cone. The passivation with hydrogen atoms influences the surface states of the topological insulator in the series HgX (X : S, Se, Te). When the dangling bonds are saturated by hydrogen, the trivial surface states disappear.

L’objectif de cette thèse était de synthétiser des multicouches à base de couches ferromagnétiques GeMn qui sont empilées et séparées par des couches de Ge en utilisant la technique d'épitaxie par jets moléculaires.Outre de nombreuses applications en spintronique issues de cette structure de matériaux, la réalisation de capteurs biochimiques dédiés à la détection moléculaire est l’idée directrice de ce travail. Un tel dispositif présenterait les atouts que ses matériaux constituants apportent : haute sensibilité, sélectivité et compatibilité parfaite avec la technologie de Si-Ge. Dans la première partie de ce manuscrit sont présentés les résultats obtenus de la croissance d’hétérostructures Mn5Ge3, Mn5Ge3Cx sur Ge(111) puis la reprise d’épitaxie de la barrière de Ge sur Mn5Ge3, la première étape avant la croissance de la deuxième couche ferromagnétique. Nous avons également analysé les propriétés structurales et magnétiques de ces couches minces ainsi que les dificultés dues à la croissance de la couche de Ge, notamment la diffusion et la ségrégation. Deux approches utilisant le carbone ont été proposées pour réduire la ségrégation : barrière de diffusion en carbone et remplissage des sites interstitiels du réseau Mn5Ge3 par du carbone. Le second axe alternatif pour la synthèse est consacré à la croissance de la structure colonnaire empilée Ge1-xMnx. Les conditions pour obtenir la structure colonnaire ont été déterminées. Les propriétés structurales et mesures magnétiques ont montré que cette phase était particulièrement intéressant dans la famille des semiconducteurs ferromagnétiques dilués à base de Ge-Mn pour les applications en spintronique et croissance de multicouches. La reprise d’épitaxie de plusieurs couches ferromagnétiques séparées par Ge a été effectuée et l’étude du couplage magnétique a été également menée. Enfin, nous présentons les premiers résultats sur le greffage de porphyrines et de protéines sur diverses surfaces hydrophiles et hydrophobes (Si, Ge), permettant d’accéder aux études de la faisabilité des capteurs Ge/GeMn. L’ensemble de ce travail indique que les multicouches de Ge/GeMn apparaissent comme des candidats à fort potentiel pour la spintronique, notamment pour capteurs bio-chimiques dans les semi-conducteurs du groupe IV. / The objective of this thesis is to synthetize the multilayers based on the sandwiched structure of GeMn ferromagnetic layers by mean of Molecular Beam Epitaxy on Ge substrate. Applications in spintronic field from this study are potential such as structures of spin valves, nanoscale sensors devoted to the detection of biochemical molecules. We actually focus on the biochemical sensors based on GMR (or TMR) phenomenon in stacking layered structure. These devices offer many advantages that the constituent materials may provide : high sensibility, selectivity, and especially, compatibility with Si-Ge technology. The first part of this manuscript presents the results obtained of heterostructure growth of Mn5Ge3, Mn5Ge3Cx on Ge(111), then Ge overgrowth on Mn5Ge3, the first step to study multilayers growth. Also, we have discussed about the structural and magnetic properties of these thin films as well as the problems due to the growth of multilayers, especially the diffusion and segregation. The approaches to reduce the diffusion were proposed by introducing carbon atoms as diffusion barrier or by fulfilling insterstial sites of Mn5Ge3 lattice by carbon atoms. The second axis of materials synthesis is devoted to the growth of multilayers Ge1-xMnx nanocolumn structure. The growth condition of Ge1-xMnx nanocolumns has been determined. We have studied structural and magnetic properties of this phase which are of particular interest to spintronic applications and multilayers growth. The Ge/Ge1-xMnx nanocolumns multilayers have been done and the interlayer exchange coupling between ferromagnetic layers has been studied. Finally, we have presented the preliminary results of porphyrin molecules and protein grafting on hydrophilic and hydrophobic surfaces (Si and Ge). This allows accessing to study the feasibility of Ge/GeMn-based sensors. This work indicates that the Ge/GeMn mutilayers appear to be a potential candidate for spintronics and biochemical sensors in the group IV semi-conductors.

Le développement de nouveaux dispositifs spintroniques à base de semi-conducteurs (SC) nécessite la création d'une population électronique polarisée en spin dans ces matériaux. De ce point de vue, le germanium est un matériau prometteur pour les applications en spintronique à cause de la forte mobilité des porteurs de charge ainsi que de la symétrie d'inversion du cristal diamant à l'origine de temps de vie de spin très longs. Dans ce manuscrit, nous discutons deux approches pour l'injection et la détection électrique de spins dans le germanium. La première approche consiste à utiliser une barrière tunnel et un métal ferromagnétique (FM) comme injecteur de spin. L'insertion d'une barrière tunnel à l'interface FM/SC permet de résoudre le problème fondamental du désaccord de conductivité. Nous avons utilisé deux injecteurs différents : Py/Al2O3 et CoFeB/MgO. Les mesures sont réalisées en géométrie à trois contacts et l'accumulation de spins dans le germanium est démontrée par la mesure de l'effet Hanle. Dans le cas d'une barrière d'Al2O3, les spins injectés s'accumulent sur des états localisés à l'interface oxyde/Ge et cette accumulation est observée jusqu'à 220 K. Dans le cas d'une barrière de MgO, les spins sont réellement injectés dans le canal de Ge et un signal de 20-30 µV est encore observé à température ambiante. Nous discutons dans la deuxième approche l'utilisation du semi-conducteur magnétique (Ge,Mn) comme injecteur de spins dans le Ge. Nous avons tout d'abord étudié les propriétés structurales et magnétiques de films minces de (Ge,Mn) fabriqués par épitaxie par jets moléculaires à basse température. En faisant varier les paramètres de croissance, nous avons pu observer des nanocolonnes de GeMn cristallines ou amorphes, ainsi que des films et des nanoparticules de Ge3Mn5. Nous nous sommes concentrés sur l'anisotropie magnétique de ces nanostructures. Finalement, la croissance de (Ge,Mn) sur GOI a été optimisée en vue de son utilisation comme injecteur de spins dans le germanium et différentes méthodes d'intégration de ce matériau dans les dispositifs de spintronique « tout semi-conducteur » sont discutées. / Creation of spin polarization in non-magnetic semiconductors is one of the prerequisite for creation of spintronics based semiconductor devices. Germanium is interesting for spintronics applications due to its high carrier mobilities and its inversion symmetry that gives long spin lifetimes. In this manuscript, we discuss two approaches for electrical spin injection and detection in Germanium. The first approach is to use a tunnel barrier and a ferromagnetic metal as a spin injector. The tunnel barrier at the interface circumvents the conductivity mismatch problem. Two different spin injectors are used: Py/Al2O3 and CoFeB/MgO. The measurements are performed in three-terminal geometry and the proof of spin accumulation is given by Hanle measurements. In case of Al2O3, the spin accumulation is predicted to be in localized states at the oxide/Ge interface and the spin signal is observed up to 220 K. However in MgO based devices, true injection in Ge channel is predicted and spin signal of 20-30 µV is observed at room temperature. The second approach of using ferromagnetic semiconductor (Ge,Mn) as spin injector is also discussed. The structural and magnetic properties of (Ge,Mn) thin-films grown by low-temperature molecular beam epitaxy (LT-MBE) are studied. Depending on the growth parameters, crystalline/amorphous GeMn nanocolumns and Ge3Mn5 thin films or nanoclusters have been observed. Magnetic anisotropy in these nanostructures is also studied. Finally, the growth of (Ge,Mn) films on GOI substrates is shown and different ways to use (Ge,Mn) as a spin injector in Ge are discussed to achieve all-semiconductor based spintronics devices.

Dans ma thèse, j’ai travaillé sur les modèles de fils en ferromagnétisme. J’ai obtenu les résultats suivants :- Existence de solutions très régulières pour les équations de Landau-Lifschitz en dimension 3.- Stabilité de profils de murs avec critère optimal de stabilité pour un fil soumis à un champ magnétique.- Stabilité de profils de murs pour un fil soumis à un courant électrique, dans le cas d’un fil à section circulaire et dans le cas d’un fil à section ellipsoïdale. - Justification des modèles monodimensionnels de fils. / In my thesis, I worked on models of wires in ferromagnetism. I got the following results:- Existence of very regular solutions for Landau-Lifschitz equations in dimension 3.- Optimal stability criterion for a wall in a ferromagnetic wire in a magnetic field.-Stability of walls in a ferromagnetic wire subjected to an electric current, in the case of a round wire and in the case of an ellipsoidal cross-section wire.- Justification of one-dimensional wires models.

Made available in DSpace on 2014-12-17T15:42:14Z (GMT). No. of bitstreams: 1 AndreiaCL_TESE.pdf: 5308625 bytes, checksum: 13df680734f410713c3992d8e7be1c8f (MD5) Previous issue date: 2010-12-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Orthoferrites AFeO3 (A = rare earth) are an important class of perovskite oxides that exhibit weak ferromagnetism. These materials find numerous applications as chemical sensors, cathodes for fuel cells and catalysis, which make them interesting from the standpoint of science and technology. Their structural, electrical and magnetic properties are dependent on many factors such as the preparation method, heat treatment conditions, chemical composition and replacement of cations in sites A and/or B. In this paper, LaFe1-xMnxO3 (0 ≤ x ≤ 1) orthoferrites-type was prepared by Pechini method and Microwave-assisted combustion reaction in order to evaluate the influence of synthesis route on the formation of oxide, as well as the effect of parcial replacement of iron by manganese and heat treatment on the magnetic properties. The precursor powders were calcined at 700?C, 900?C, 1100?C and 1300?C for 4 hours and they were characterized by the techniques: Thermogravimetric analysis (TGA), X ray diffraction (XRD), Refinement by Rietveld method, Scanning electron microscopy (SEM), Reduction temperature programmed (RTP) and Magnetic hysteresis measurements performed at room temperature. According to the XRD patterns, the formation of perovskite phase with orthorhombic structure was observed for the systems where 0 ≤ x ≤ 0.5 and rhombohedral for x = 1. The results also showed a decrease of lattice parameters with the parcial replacement of iron by manganese and consequently a reduction in cell volume. The hysteresis curves exhibited weak ferromagnetism for the systems prepared by both synthesis methods. However, a dependence of magnetization as a function of dopant content was observed for samples produced by Pechini method. As for the systems prepared by combustion reaction, it was found that the secondary phases exert a strong influence on the magnetic behavior / Ortoferritas AFeO3 (A = terra rara) constituem uma importante classe de ?xidos perovskita que exibem ferromagnetismo fraco. Estes materiais encontram in?meras aplica??es como sensores qu?micos, catodos para c?lulas a combust?veis e na ?rea de cat?lise, o que os fazem interessantes do ponto de vista cient?fico e tecnol?gico. Suas propriedades estruturais, el?tricas e magn?ticas s?o dependentes de v?rios fatores tais como: o m?todo de prepara??o, condi??es do tratamento t?rmico, composi??o qu?mica e substitui??o de c?tions nos s?tios A e/ou B. Neste trabalho, ortoferritas do tipo LaFe1-xMnxO3 (0 ≤ x ≤ 1) foram preparadas pelo m?todo Pechini e pela rea??o de combust?o assistida por microondas com a finalidade de avaliar a influ?ncia da rota de s?ntese na forma??o do ?xido, assim como o efeito da substitui??o parcial do ferro por mangan?s e do tratamento t?rmico nas propriedades magn?ticas. Os p?s precursores foram calcinados a 700?C, 900?C, 1100?C e 1300?C por 4 horas e caracterizados atrav?s das t?cnicas: An?lise termogravim?trica (TG), Difra??o de raios X (DRX), Refinamento pelo m?todo de Rietveld, Microscopia eletr?nica de varredura (MEV), Redu??o a temperatura programada (RTP) e Medidas de histerese magn?ticas realizadas ? temperatura ambiente. De acordo com os difratogramas, a forma??o da fase perovskita com estrutura ortorr?mbica foi observada para os sistemas onde 0 ≤ x ≤ 0,5 e, rombo?drica para x = 1. Os resultados tamb?m mostraram uma diminui??o dos par?metros de rede com a substitui??o parcial do ferro por mangan?s e, conseq?entemente uma redu??o do volume da c?lula unit?ria. As curvas de histerese exibiram ferromagnetismo fraco para os sistemas preparados por ambos os m?todos de s?ntese. Entretanto, uma depend?ncia da magnetiza??o em fun??o do teor de dopante foi observada para as amostras produzidas pelo m?todo Pechini. J? para os sistemas preparados por rea??o de combust?o, verificou-se que as fases secund?rias exercem forte influ?ncia no comportamento magn?tico

<p>Thin metal films have found their use in many magnetic devices. They form pseudo two-dimensional systems, where the mechanisms for the magnetic interactions between the layers are not completely understood. Layered crystal structures have an advantage over such artificial systems, since the layers can be strictly mono-atomic without any unwanted admixture. In this study, some model systems of layered magnetic crystal structures and their solid solutions have been investigated by x-ray and neutron diffraction, Mössbauer and electron spectroscopy, heat-capacity and magnetic measurements, and first-principle electronic structure calculations, with the goal of deepening our understanding through controlled chemical synthesis.</p><p>The compounds TlCo₂S₂, TlCo₂Se₂ and their solid solution TlCo₂Se_2-xS_x, all containing well separated cobalt atom sheets, order with the moments ferromagnetically aligned within the sheets. In TlCo₂S₂, the net result is ferromagnetism, while TlCo₂Se₂ exhibits antiferromagnetism. The inter-layer distance is crucial for the long-range coupling, and it was varied systematically through Se-S substitution. The incommensurate helical magnetic structure found for TlCo₂Se₂ (x = 0) prevails in the composition range 0 ≤ x ≤ 1.5 but the pitch of the helix changes. The accompanying reduction in inter-layer distance on sulphur substitution varies almost linearly with the coupling angle of the helix. An additional competing commensurate helix (90°) appears in the medium composition range (found for x = 0.5 and 1.0).</p><p>The systems TlCo_2-xMe_xSe₂ show helical magnetic ordering for Me = Fe or Cu, while a collinear antiferromagnetic structure occurs for Me = Ni. Magnetic order is created by iron substitution for copper in the Pauli paramagnetic TlCu₂Se₂, but now with the moments perpendicular to the metal sheets.</p><p>TlCrTe₂ forms a quite different crystal structure, with intra-layer ferromagnetic alignment and net collinear antiferromagnetism. In contrast to the other phases, the values of the moments conform well to a localised model for Cr³⁺.</p>