Le but de la thèse sera d'étudier la faisabilité d'un nouveau procédé de nanostructuration des jonctions tunnel de dimension sub-30nm récemment imaginé et breveté par Spintec et le LTM et de tester les propriétés des jonctions tunnel obtenus sur les plans structural, magnétique et des propriétés électriques. Une attention particulière sera mise sur la caractérisation des défauts générés en bord de piliers lors de la gravure des jonctions tunnels et l'impact de ces défauts sur les propriétés magnétiques et de transport. Une autre partie de la thèse concerne l'optimisation des propriétés magnétiques et de transport des empilements jonctions tunnel magnétiques en vue d'en améliorer la stabilité thermique, l'amplitude de magnétoresistance tunnel et la facilité de gravure de l'empilement.En particulier l'insertion de nouveaux matériaux réfractaires (W, ) dans les empilements a été étudiée pour améliorer la stabilité de l'empilement lors des recuits à haute température. Des améliorations ont également été apportées pour renforcer la stabilité de la couche de référence de la jonction tunnel lorsque cette dernière est située au dessus de la barrière tunnel. Par ailleurs, une nouvelle couche de couplage antiferromagnétique a été mise au point permettant de réduire significativement l'épaisseur totale de l'empilement et par là même facilitant sa gravure.Tous ces résultats ont été obtenus par des mesures magnétiques et de transport réalisées sur les couches continues et sur des piliers de taille nanométriques. / The first aim of the thesis is to study the feasibility of a new process for nanopatterning of sub-30nm diameter tunnel junctions recently patented by Spintec and LTM and to test the properties of tunnel junctions obtained, from the point of view of magnetic and electrical properties. Particular attention will be paid on the characterization of defects generated at the pillar edges when patterning the tunnel junctions and the impact of these defects on the magnetic and transport properties. Another part of the thesis is focused on improving the magnetic and transport MTJ stacks with higher thermal budget tolerance. As a part of this, new materials (W, etc) were used as cap layer or as a spacer layer in composite free layer of pMTJ stacks. Moreover, different magnetic materials combined with different non-magnetic spacer have been investigated to improve the thermal stability factor of the composite storage layers. Detailed structural characterizations were performed to demonstrate the improvements in magnetic and electrical properties. A new RKKY coupling layer was found which allowed to obtain an extremely thin pMTJ stack by reducing the SAF layer thickness to 3.8nm. Seed lees multilayers with enhanced PMA is necesssary to realize a top-pinned pMTJ stack which is necessary to configure a spin-orbit torque MRAM (SOT-MRAM)stack and double magnetic tunnel junction stacks (DMTJs). A new seed less multilyar with enhanced PMA and subsequently advanced stacks such as conventional-DMTJ, thin-DMT, SOT-MRAM stacks, Multibit memory were realized. Finally, electrical properties patterned memory devices were also studied to correlate with the magnetic properties of thin films.

The exploitation of colloidal building blocks with morphological and functional anisotropy facilitates the generation of complex structures with unique properties, which are not exhibited by isotropic particle assemblies. Herein, we demonstrate an easy and scalable bottom-up approach for the programmed assembly of hairy oppositely charged homogeneously decorated and Janus particles based on electrostatic interactions mediated by polyelectrolytes grafted onto their surface. Two different assembly routes are proposed depending on the target structures: raspberry-like/half-raspberry-like or dumbbell-like micro-clusters. Ultimately, stable symmetric and asymmetric microstructures could be obtained in a well-controlled manner for the homogeneous–homogeneous and homogeneous–Janus particle assemblies, respectively. The spatially separated functionalities of the asymmetric Janus particle-based micro-clusters allow their further assembly into complex hierarchical constructs, which may potentially lead to the design of materials with tailored plasmonics and optical properties.

In this master ‘s thesis, catanionic vesicles formed by the pseudo-double-chain complex CTA – DS were investigated from the point of view of microviscosity. Samplesand of cationic vesicles contained 23, 43 and 53 mol. % of cholesterol and the double-chain surfactant DODAC. Cationic vesicles were prepared for visual observation, their stability was determined by DLS and the prepared system was further investigated. Microviscosity was determined from fluorescence anisotropy. To study the outer part of the membrane, laurdan fluorescent probes were used whereas diphenylhexatriene was used for the inner part of the membrane. This method has been proven to be suitable because it reflects the conditions of the membrane. Moreover, a 1,3-bispyrenylpropane probe forming intramolecular excimers was used to study the microviscosity in the vesicle bilayer. The dicyanovinyljulolidine (DCVJ) probe was applied in the case of the molecular rotor technique. It has been shown that in the case of the DCVJ probe, the molecular rotor technique is practically unusable, due to the fact that the probe has a low quantum yield at low temperatures. Also, the excimer formation of P3P probes does not lead to the expected results. The cationic vesicles do not seem to support this formation, as they are too closely related. This type of probe can be used for the selected system with some restrictions.

The first objective of this thesis was compiling research about currently produced pistons for internal combustion engines and about additive manufacturing and based on the acquired information deciding which type of piston makes the most of the advantages. Following this research, the next step was creating a design adjustment of a piston, which was previously designed with the conventional methods of manufacturing in mind, in a way that would make the best use of the different possibilities of additive manufacturing. There was also an optimisation carried out, which depicted the densities of material elements in the piston, showing where the material was less important. There were three variants of the additive manufactured piston created, ranging from a relatively conservative design, which could be theoretically produced by conventional methods with a more substantial subtraction of material added, to a design which could only be produced via additive manufacturing. A thermo-structural analysis at maximum engine load was carried out for all these piston models. Based on these data, a conclusion was made, whether the use of additive manufacturing was justified over the use of the conventional subtractive methods.

Biological tissues are optically inhomogeneous and absorbent materials. They are comprised of various structures such as cells, cell organelles, and various fiber structures. Due to these structures leads to different interactions with the light and phenomena such as absorption, scattering and polarization of light. Different ultrasonic, electromagnetic, electrical and optical methods are used for meat ageing detection. Muscles are turbid anisotropic media, they exhibit changes in electrical and optical properties according to the direction of the electrical and optical fields in the sample. The diploma work assesses the feasibility of impedance measurements for meat ageing detection and their comparison with optical measurement of scattered polarized light. Two different sample were used: pork chop slices and chicken breasts were used for their relative homogeneity. The electrical method is a promising method due to the possibility of getting much information and realizing cheap and fast enough measurement systems. The proposed optical method allows measure the rotation of polarization plane with meat ageing in the range of 95 degrees within considered period. Through the first promising results obtained in this thesis, a further work has to be provided to determine closer relationship between optical scattering characteristics, electrical anisotropy in ageing-related tissue structural properties.

Dans cette étude, nous analysons les conséquences mécaniques des transformations de phase diffusives, particulièrement la plasticité de transformation ou TRIP (TRansformation Induced Plasticity) ainsi que le comportement élasto-viscoplastique. Cette plasticité de transformation, explicable par le mécanisme de Greenwood-Johnson, est souvent décrite avec le modèle de Leblond qui fait l'hypothèse d'un comportement élastoplastique. Dans ce modèle comme dans la majorité des analyses expérimentales et des modélisations (analytiques, par éléments finis, FFT ou encore champ de phase), une des hypothèses principales est de ne pas prendre en compte le caractère visqueux du comportement. Or plusieurs études récentes montrent que le comportement des deux phases (parente et produite) peut être très sensible au taux de déformation imposé, particulièrement à haute température. D'où l'intérêt de développer une modélisation rendant compte des effets visqueux présents lors de certaines transformations. Pour ce faire, nous adoptons une modélisation numérique où le comportement de chaque phase est décrit par une loi élasto-viscoplastique à écrouissage mixte associée à la loi de Norton ; la cinétique de transformation est imposée et le problème d'interactions mécaniques entre phases est traité par la méthode des éléments finis. D'une part, la contribution de la viscosité au TRIP est quantifiée pour différents taux de déformation imposés durant la transformation de phase. D'autre part, l'effet du taux de transformation (configuration arbitraire) sur la prédiction du TRIP est évalué et caractérisé. Une extension des modèles existants (à cinétique périodique et aléatoire) est proposée. Elle consiste d'abord à étudier et évaluer l'effet de la morphologie de germe ainsi que l'anisotropie de croissance sur la prédiction du TRIP. Ensuite, une amélioration avec un modèle anisotherme, basé sur des mesures expérimentales existantes, a été introduite. Elle consiste principalement à tenir compte de la variation des propriétés mécaniques en fonction de la température. Les analyses montrent que la prise en compte de la viscosité peut conduire à des effets importants sur la prédiction du TRIP par rapport aux résultats obtenus avec un modèle élastoplastique classique. Elles montrent en particulier, en configuration anisotherme, une amélioration de la prédiction du TRIP mesuré expérimentalement lors de la transformation perlitique d'un acier 100Cr6 [Tahimi, 2012]. Cette étude permet par ailleurs de dégager des tendances évidentes dans les relations entre le TRIP et l'histoire de la transformation : chargement mécanique et cinétique de transformation, morphologie des germes et anisotropie de croissance. Ces résultats pourront contribuer à l'élaboration d'un modèle analytique simple prenant en compte la viscosité. / In this study, the mechanical consequences of phase transformations in steel, particularly, the TRansformation Induced Plasticity TRIP as well as the elasto-viscoplastic behavior has been analyzed. This transformation plasticity, due to the Greenwood-Johnson mechanism, is often described with the model of Leblond with the assumption of an elastoplastic behavior. Moreover, in the majority of experimental analysis or numerical finite elements modeling FEM or phase field modeling PFM, the viscous criteria were not considered. However, several recent studies have demonstrated that both phases (parent and product) show high strain-rate sensitivity at elevated temperatures. Hence, the principal interests using the FEM modeling to extend these main reference models of [Leblond, 89] and [Taleb-Sidoroff, 2003], with taking into account the viscous effects, which are present during some phase transformations, especially at high temperatures. To do this, the behavior of each phase is described by an elasto-viscoplastic law with mixed hardening associated to the Norton law. The transformation kinetics is imposed and the problem of mechanical interactions between phases is processed by the finite element method. On the one hand, the contribution from viscosity to TRIP was quantified for different strain-rate during phase transformation. On the other hand, the effect of an arbitrarily-set of transformation-rate in the FEM simulations was evaluated and characterized. An extension of the existing models (for periodic and random kinetics) is proposed. It consists at first in studying and in evaluating the effect of both the morphology of nuclei and the growth anisotropy, on the prediction of TRIP. Then, an improvement with non-isothermal model, based on existing experimental measures, was introduced. It consists mainly in taking into account the variation of the mechanical properties of the mixture of both phases, according to the temperature. The predictions show that in such cases, the consideration of the viscosity can lead to major changes of the estimated TRIP compared with results obtained from a classic plastic model. Also, the prediction of TRIP can be significantly influenced by the choice of the morphology of germs and by the type of growth: isotropic or anisotropic. These improvements, particularly with the non-isothermal configuration, show a good agreement with experimental measures of TRIP on the 10006 steel during pearlite phase transformation [Tahimi, 2012]. This study allows besides, releasing obvious trends in the relations between the TRIP and the history of the phase transformation: mechanical loading and kinetics of transformation, morphology of nuclei and growth anisotropy. These results can contribute to the elaboration of a simple analytical model taking into account the viscous criteria.

L’objectif consistant à élaborer des «aimants par conception» peut être atteint en adaptant les structures moléculaires des complexes de coordination. Les molécules conçues devraient présenter les caractéristiques requises pour des applications spécifiques, qui résultent de leur riche diversité structurale. Des complexes mononucléaires à base de Ni avec une grande anisotropie magnétique et des molécules polynucléaires à base de Ni et de Co sont préparés et étudiés dans cette thèse. Les synthèses, les études magnétiques et les propriétés électrochimiques des complexes contenant un ligand pontant non innocent sont étudiées. Les complexes mononucléaires Ni(II) à géométrie bipyramide trigonale sont préparés avec des ligands axiaux et les contre-anions différents. L'effet de la nature des ligands axiaux et du changement structural induit par les contre-anions sur l'anisotropie magnétique est étudié expérimentalement et analysé à l'aide de calculs théoriques. Des molécules organiques sont utilisées pour concevoir des complexes trinucléaires à grande anisotropie magnétique et à couplage d'échange faible. Plusieurs complexes polynucléaires à base de Ni et de Co où le TTC³⁻ agit comme un ligand pontant innocent et le HHTP³⁻ comme un ligand non innocent typique sont cristallisés avec diverses structures (TTC = Trithiocyanurate; HHTP = Hexahydroxytriphénylène). Pour les complexes contenant le ligand non innocent (HHTP), les anions radicalaires sont produits par électrochimie. La combinaison de la spectro-électrochimie et de la spectroscopie à résonance paramagnétique électronique couplée à des études d'électrochimie permet d'étudier la délocalisation des électrons sur les radicaux organiques générés et le couplage d'échange entre les ions métalliques. / The objective of elaborating “magnets by design” can be achieved by tailoring the molecular structures of coordination complexes. The designed molecules are expected to exhibit the characteristics required for specific applications, virtually resulting from their rich structural diversity. Mononuclear Ni-based complexes with large magnetic anisotropy and polynuclear Ni- and Co-based molecules are designed in this dissertation. The syntheses, magnetic studies, and electrochemical properties of the complexes containing non-innocent bridge ligand are investigated. The Ni(II) mononuclear complexes with trigonal bipyramid geometry are prepared by tuning the axial ligands and the counter anions. The effect of the nature of the axial ligands and the structural change induces by the counter anions on magnetic anisotropy is studied experimentally and analyzed with the help of theoretical calculations. Large organic molecules are used to design trinuclear complexes with large magnetic anisotropy and weak exchange coupling. Several polynuclear Ni- and Co-based complexes with TTC³⁻ acting as an innocent bridging ligand and HHTP as a typical non-innocent ligand, are crystallized with various structures (TTC = Trithiocyanurate; HHTP = Hexahydroxytriphenylene). For the complexes containing the non-innocent ligand (HHTP), radical anions are produced by electrochemistry. The combination of spectroelectrochemical and Electron Paramagnetic Spectroscopy coupled to electrochemistry studies allow investigating the delocalization of the electrons on the generated organic radicals and the exchange coupling among the metal ions.

Magnetic nanoparticles have received extensive attention in the biomedical research, e.g. as prospective contrast agents for T2-weighted magnetic resonance imaging. The ability of a contrast agent to enhance the relaxation rate of 1 H in its vicinity is quantified by relaxivity. The main aim of this thesis is to evaluate the transversal re- laxivity of ε-Fe2−x Alx O3 nanoparticles coated with amorphous silica or citrate - its dependence on external magnetic field, temperature and thickness of silica coating - by means of nuclear magnetic resonance. The aluminium content x = 0.23(1) was determined from XRF, the material was further characterised by XRPD, Möss- bauer spectroscopy, DLS, TEM and magnetic measurements. The size of magnetic cores was ∼ 21 nm, the thickness of silica coating ∼ 6,10,17 and 21 nm. Magne- tization of the ε-Fe2−x Alx O3 nanoparticles increased by ∼ 30 % when compared to ε-Fe2O3. The saturating dependence of relaxivity on external magnetic field and on the linear decrease with increase of thickness of silica coating contravene the theo- retical model of motional averaging regime (MAR); nevertheless, the temperature dependence acquired in 0.47 T and 11.75 T may be explained by MAR. In compari- son to ε-Fe2O3 nanoparticles, the relaxivity of examined samples was higher for par-...

Modification of interfaces in nanostructures can significantly influence their overall properties. Magneto-optical spectroscopy and spectroscopic ellipsometry are ideal for studying these phenomena thanks to their in-depth sensitivity and contactless measurements. Two methods of nonreversible modification of magnetic properties, especially the magnetic anisotropy, are investigated. The measured spectral dependence of magneto-optical Kerr effect is compared to a theoretical calculation in order to determine the profile of the samples for different levels and methods of modification. In addition to this, ellipsometric measurements are performed on a device whose optical properties change by voltage application.

Title: Ground state investigations of Ce and U intermetallic compounds Author: Attila Bartha Department: Department of Condensed Matter Physics Supervisor: RNDr. Jan Prokleška, Ph.D., Department of Condensed Matter Physics Abstract: Rare earth and actinide intermetallic compounds offer a plethora of interesting physical properties due to the varied behavior of f -electrons together with numerous interactions these electrons are exposed to. In this thesis we address a broad spectrum of ground state investigations on CePd2X3 (X=Zn, Ga) and (Ce,U)nTIn3n+2 (T=Rh, Ir) compounds. Single crystals of CePd2Zn3 and CePd2Ga3 compounds were synthesized for the first time using Bridgman method. CePd2Ga3 revealed a ferromagnetic transition with TC = 6.7 K with a strong magnetocrystalline anisotropy. CePd2Zn3 orders antiferromagnetically below TN = 1.9 K. Results of magnetization measurements on Ce2IrIn8 revealed effective magnetic moment µeff = 2.45µB/Ce3+ and a paramagnetic Curie temperature θP = −31 K. Decomposition of Hall resistivity ρxy(B) into NHE and AHE revealed a predom- inance of AHE in the temperature range from 60 K up to 100 K. Ce2RhIn8 was studied by means of magnetic field and angle dependent magnetization and heat capacity measurements. The resulting phase diagram reveals a complete unfold- ing and...