The crystalline iron-based nanowires encapsulated by multiwalled carbon nanotubes have been the subject of numerous studies owing to the range of potential applications. The presence of a-Fe (bcc)/y -Fe(fcc) junctions o ers the possibility of exploitation of the exchange bias effect, an interfacial magnetic phenomenon that plays a major role in magnetocaloric cooling, spintronic and high-density magnetic storage devices. This work is concerned with the synthesis and microstructural characterization of Fe-based and NiFe nanowires encapsulated by multiwall carbon nanotube radial structures. The known attributes of these structures are well matched to the magnetocaloric application. The primary aim of this work was to determine the unknown microstructural details of the encapsulated nanowire that are of relevance to the magnetocaloric application (junction types, location and orientation relative to the nanotube axis). The secondary aim was to explore the modi cation of the synthesis route to promote desirable attributes. This is the first report of a-Fe/y -Fe sequential junctions and a-Fe/Fe3C concentric junctions in encapsulated Fe-based nanowires. The presence of a-Fe/y -Fe junctions was inferred from the observation of a-Fe nanowires terminated by a ~100 nm length y-Fe crystallites of larger diameter. The a-Fe/Fe3C junctions exhibit the Bagaryatski orientation relationship: [110 ]bcck[100 ]orth. The degree of substrate roughness was found to be a means of tailoring details of the structure and composition of the encapsulated nanowires. NiFe encapsulated nanowires were found to contain crystallites of a-NiFe, y-NiFe and Ni3Fe and the sequential junctions -NiFe/Ni3Fe and a-NiFe/y-NiFe junctions.

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

Nanostructured systems composed of two or more technologically important materials are useful for device applications and intriguing for the new fundamental physics they may display. Magnetism at the nanoscale is dominated by size and surface effects which combined with other media lead to new spin dynamics and interfacial coupling phenomena. These new properties may prove to be useful for optimizing sensors and devices, increasing storage density for magnetic media, as well as for biomedical applications such as drug delivery, MRI contrast enhancement, and hyperthermia treatment for cancer. In this project we have examined the surface and interface magnetism of composite nanoparticles and multilayer thin films by using conventional DC magnetization and AC susceptibility as well as transverse susceptibility, a method for directly probing the magnetic anisotropy of materials. Au and Fe3O4 synthesized together into three different nanoparticle configurations and ranging in size for 60 nm down to 9nm are used to study how the size, shape, and interfaces affect the most fundamental properties of magnetism in the Au-Fe3O4 system. The findings have revealed ways in which the magnetic properties can be enhanced by tuning these parameters. We have shown that by changing the configurations of the Au and Fe3O4 particles, exotic behavior can be observed such as a large increase in anisotropy field (H[subscript]K ranging from 435 Oe to 1650 Oe) and the presence of exchange bias. Multilayer thin films have been studied as well which combine the important classes of ferromagnetic and ferroelectric materials. In one case, barium hexaferrite/barium strontium titanate thin films, the anisotropic behavior of the ferromagnet is shown to change due to the introduction of the secondary material. In the other example, CrO2/Cr2O3 bilayers, exchange coupling is observed as Cr2O3 is an antiferromagnet as well as a ferroelectric. This coupling is manifest as a uniaxial anisotropy rather than the unidirectional anisotropy associated with exchange biased bilayers. Not only will such multifunctional structures will be useful for technological applications, but the materials properties and configurations can be chosen and tuned to further enhance the desired functional properties.

Cette thèse présente une étude de l'anisotropie magnétique de semiconducteurs ferromagnétiques en couches minces et du couplage magnétique dans des bicouches formées à partir de ces matériaux et de métaux ferromagnétiques. Je me suis focalisé sur deux systèmes distincts : des films minces de l'alliage quaternaire GaMnAsP et des bicouches : MnAs/GaMnAs. Dans ces systèmes, j'ai étudié l'influence sur les anisotropies magnétiques d'une part, de la déformation biaxiale induite par le désaccord de maille avec le substrat et d'autre part, de la concentration en trous. Ces études ont été menées principalement par résonance ferromagnétique, mesures d'aimantation par SQUID, ainsi que grâce à des mesures de transport et de diffraction de rayons X à haute résolution. Deux séries de films de GaMnAsP caractérisées par des concentrations en Mn de 7% et 10% ont été étudiées. Pour chaque série, la concentration en P a été variée sur une large gamme de 0 à 20%. Les forts dopages en P sont intéressants car le régime de conduction peut changer, passant de métallique à bande d'impuretés. Ceci induit de profondes modifications de tous les paramètres magnétiques pertinents. Nous avons étudié les variations d'anisotropie magnétique avec la concentration en P. Une réorientation de l'aimantation avec la température a pu être mise en évidence pour une concentration 6% P. Des mesures de RFM à haute fréquence ont permis d'étudier l'anisotropie magnétique de films de MnAs épitaxiés sur (111) et (100) GaAs. Un couplage d'échange ferromagnétique est mis en évidence pour les bicouches MnAs/GaMnAs. La relaxation de l'aimantation de ces systèmes a été étudiée via le facteur de Gilbert, déterminé à partir de l'étude de la largeur des résonances en fonction de la fréquence des microondes utilisées.

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 non reportée jusqu'à présent dans la littérature. 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 eu 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. Cette étude a ainsi montré la nécessité de prendre en compte le champ dipolaire- habituellement négligé- dans l'analyse des figures de diffusion.

Hole-doped manganite La0.7Ca0.3MnO3 (LCMO) was extensively studied because of its colossal magnetoresistance (CMR) characteristic in a magnetic field. Recently, a new member of CMR family La0.7Ce0.3MnO3 (LCeMO), an electron-doped manganite, raises a new wave of attention for possible application in p-n junction. In this present study, LCMO and LCeMO single layer and bi-layer were grown on SrTiO3 (100) substrate by a pulse laser ablation technique. Due to the neutralization at the p-n junction a possible insulating layer with the anti-ferromagnetic (AFM) property is expected. There is no systematically study of this matter up to date, thus, it is worth to systematically investigate the physical properties of this junction. The result indicates the possible neutralization layer exhibits huge resistance comparison with two lateral layers, the bias current is constrained on the limited thickness of the top layer, which implies the neutralization layer forms a depletion layer that block the current to flow through to the bottom layer. Its electric and magnetic properties may similar to the parent compound LaMnO3 with insulating and anti-ferromagnetic characteristics. Separated by this possible layer, the magnetic coupling between lateral layers is weak. However, the possible AFM layer does pin the magnetic moment of the top layer along the direction perpendicular to the substrate that make a distinct magnetoresistance at low magnetic field.

Collective magnetic behavior in nanostructures is a phenomenon commonly observed in various magnetic systems. It arises due to competing inter/intra–particle interactions and size distribution and can manifest in phenomena like magnetic freezing, magnetic aging, and exchange bias (EB) effect. In order to probe these rather complex phenomena, conventional DC and AC magnetic measurements have been performed along with radio–frequency transverse susceptibility (TS) measurements. We also demonstrate the magnetic entropy change as a parameter sensitive to subtle changes in the magnetization dynamics of nanostructures. The focus of this dissertation is to study the collective magnetic behavior in core-shell nanostructures of Fe/γ–Fe2O3 and Co/CoO, La0.5Sr0.5MnO3 nanowires, and LaMnO3 nanoparticles. In the case of core/shell Fe/γ–Fe2O3, we found the particles to critically slow down below the glass transition temperature, below which they exhibit aging effects associated with a superspin glass (SSG) state. We demonstrate that it is possible to identify individual magnetic responses of the Fe core and the γ–Fe2O3 shell. Consistently, a systematic study of the magnetocaloric effect (MCE) in the Fe/γ–Fe2O3 system reveals the development of inverse MCE with peaks associated with the individual magnetic freezing of the core and the shell. From these obtained results, we establish a general criterion for EB to develop in core/shell nanostructures, that is when the core is in the frozen state and the magnetic moments in the shell begin to block. This criterion is shown to be valid for both ferromagnetic/ferrimagnetic (FM/FIM) Fe/γ–Fe2O3 and ferromagnetic/antiferromagnetic (FM/AFM) Co/CoO core–shell nanostructures. We also elucidate the physical origin of the occurrence of asymmetry in field-cooled hysteresis loops and its dependence on magnetic anisotropy in the Co/CoO system by performing a detailed TS study. We have performed a detailed magnetic study on hydrothermally synthesized single crystalline La0.5Sr0.5MnO3 nanowires. The temperature and field dependent evolution of the different magnetic phases leading to development of the inverse MCE and EB in the nanowires is discussed. Finally, we have studied the collective magnetic behavior of LaMnO3 nanoparticles synthesized by the sol–gel technique. The nanoparticle ensemble shows the unusual co–existence of super-ferromagnetism (SFM), as well as the SSG state, which we term the 'ferromagnetic superglass' (FSG) state. The existence of FSG and the characteristics of its magnetic ground state are discussed.

Το φαινόμενο της μαγνητικής πόλωσης ανταλλαγής (exchange bias, EB) έχει προσελκύσει το επιστημονικό ενδιαφέρον εξαιτίας των σημαντικών εφαρμογών σε διατάξεις μαγνητικής αποθήκευσης πληροφορίας. Ιδιαίτερο ενδιαφέρον εμφανίζουν οι ΕΒ ιδιότητες των πολυστρωματικών φιλμ με σύσταση [La2/3Ca1/3MnO3(FM)/La1/3Ca2/3MnO3(AF)]15, που αποτελούνται από αντισιδηρομαγνητικά, La1/3Ca2/3MnO3 (AF), και σιδηρομαγνητικά, La2/3Ca1/3MnO3 (FM), στρώματα επειδή αυτή η κατηγορία ενώσεων ανήκει στα ισχυρώς συσχετιζόμενα ηλεκτρονικά συστήματα (strongly correlated electronic systems), όπου οι μαγνητικές-, ηλεκτρονικές-, και κρυσταλλικές-δομές αλληλεπιδρούν ισχυρά μεταξύ τους. Στην παρούσα διατριβή χρησιμοποιήθηκαν μετρήσεις περίθλασης και σκέδασης συντονισμού ακτίνων-Χ στην Κ-ακμή του Mn για την μελέτη της επίδρασης των ελαστικών τάσεων επιταξίας στο μηχανισμό της μαγνητικής πόλωσης ανταλλαγής της πολυστρωματικής δομής [La2/3Ca1/3MnO3/La1/3Ca2/3MnO3]15 που εμφανίζεται κάτω από την θερμοκρασία εμπλοκής ΤΒ≈80 Κ. Οι μετρήσεις περίθλασης ακτίνων-Χ έδειξαν ότι ο λόγος c/a, που αποτελεί το μέτρο της τετραγωνικής πλεγματικής παραμόρφωσης της ψευδοκυβικής δομής, φθάνει στην μέγιστη τιμή της, και ότι το μήκος συσχετίσεως εντός των (101) και (102) κρυσταλλογραφικών επιπέδων μεταβάλλεται σημαντικά κοντά στην ΤΒ. Αυτό το φαινόμενο οφείλεται στο γεγονός ότι στην ΤΒ η ψευδοκυβική πλεγματική σταθερά aML του φιλμ προσεγγίζει την τιμή της ψευδοκυβικής πλεγματικής σταθερά της ένωσης La1/3Ca2/3MnO3 από την οποία αποτελούνται τόσο το ενδιάμεσο στρώμα (buffer layer) όσο και τα AF στρώματα, αποδεικνύοντας έτσι ότι το EB φαινόμενο σχετίζεται με την εξισορρόπηση των επιταξιακών τάσεων εντός των AF και FM στρωμάτων. Οι μετρήσεις σκέδασης συντονισμού ακτίνων-Χ (RXS) αποκαλύπτουν ότι οι επιταξιακές τάσεις εξωθούν τα πολύεδρα MnO6 σε σιδηροπαραμορφωτική (ferrodistortive, FD) ευθυγράμμιση, όπου η FD υπερκυψελίδα συμπίπτει με την μοναδιαία κυψελίδα της κρυσταλλικής δομής. Εφαρμογή της τεχνικής συμβολής στα RXS φάσματα αποκαλύπτει μια κορυφή συντονισμού από την κύρια ακμή απορρόφησης των ιόντων Mn στα ~6.555 keV και μια, μικρότερης έντασης, δευτερεύουσα κορυφή συντονισμού στα ~6.55 keV, του οποίου η ενεργειακή μετατόπιση ελαττώνεται γραμμικά με την θερμοκρασία και το λόγο c/a μέχρι τους 80 Κ. Η εξαφάνιση της δευτερεύουσας κορυφής πάνω από τους 80 Κ(≈ΤΒ) μπορεί να σχετίζεται με κάποια αναδιάταξη των γωνιών που σχηματίζουν οι δεσμοί Mn-O-Mn εξαιτίας της εξισορρόπησης των επιταξιακών τάσεων στις FM/AF διεπιφάνειες κάτω από 80 Κ. / The exchange bias (EB) phenomenon has received considerable attention because of its important applications in magnetic storage devices. Of particular interest are the EB properties of colossal magnetoresistance (CMR) compositionally modulated structures consisting of antiferromagnetic (AF) and ferromagnetic (FM) (La,Ca)MnO3 layers because manganites are strongly correlated electron systems, in which the magnetic, electronic and crystal structures interact strongly with each other. Complementary x-ray synchrotron radiation diffraction (XRD) and resonant scattering (RXS) measurements were performed at the Mn K-edge between 10 and 300 K in order to analyze the effect of epitaxial strain and tetragonal lattice distortions on the exchange bias (EB) mechanism observed in [La2/3Ca1/3MnO3(FM)/La1/3Ca2/3MnO3(AF)]15 multilayers below a blocking temperature, TB, of 80 K. XRD measurements showed that the c/a axial ratio, an indication of the tetragonal lattice distortion in pseudocubic lattice settings, reaches its maximum at the onset of the EB effect and the corresponding structural correlation length varies substantially at the onset of TB. The in-plane lattice parameter a at TB is close to the bulk lattice parameters of the AF layers, thus indicating that the EB effect is related with the accommodation of strain inside the FM and AF layers. RXS measurements revealed that such anisotropic lattice strains force the MnO6 octahedral sites into a ferrodistortive (FD) alignment, where the FD supercell coincides with the unit cell of the crystalline lattice. The RXS intensity difference signal exhibits a main-edge feature and a post-edge feature at 6.57 keV that scales linearly with temperature and the c/a ratio up to 80 K. The disappearance of the post-edge feature above 80 K(=TB) may signify a rearrangement of Mn-O-Mn bonding angles due to strain-driven effects at the FM/AF interfaces, inducing disorder in FD octahedral tilt ordering which may pin the local distortions below the TB.

The magnetic properties and crystal texture of micron-sized, lithographically patterned ferromagnetic/antiferromagnetic (FM/AF) exchange-coupled elements supporting vortex remanent magnetization states were characterized using experimental and numerical modeling techniques. 10umx10um square elements consisting of Ni80Fe20/Ir20Mn80 bilayers prepared on silicon and glass substrates using e-beam lithography and magnetron sputtering were thermomagnetically annealed under various in-plane cooling fields to induce exchange bias. Longitudinal and time-resolved Kerr effect microscopy were employed to measure the quasi-static hysteresis and dynamic response, while X-ray diffraction analysis was used to probe their crystal texture under different deposition and substrate conditions. The FM layer was found to be critical for the development of the necessary texture and spin alignment in the AF for creating interfacial exchange-bias. The exchange-bias field was found to significantly alter the magnetic behavior of the samples, leading to the stabilization of the vortex structure and asymmetric hysteresis loop shift in the quasi-static regime, as well as precessional frequency reduction of the bottom domain in the dynamic regime. Numerical simulations showed good qualitative agreement with both experimental observations and existing literature, and revealed the origin of the precessional frequency reduction as the different spin-wave eigenmodes excited by different remanent magnetization states. / Graduate

Magnetic films have gained great attention for decades because of their broad industrial application. Their modern functionality more and more relies on their domain structure. Magnetic films usually form complex domain patterns with unique structures at different length scales due to the competition between short range attractive and long range repulsive interactions. The ensemble of domains is topologically disordered, although each of them possesses orientational spin order. Since simplifying complexity is the key step to understand and transform nature, finding new orders from the ostensible disordered structures would be a fascinating topic. Scattering techniques are well-known powerful tools to detect orders. Coherent soft xray magnetic resonant scattering becomes accessible with the development of synchrotron radiation facilities. We applied the technique to study the domain structure of CoPd/MnIr multilayer films with perpendicular magnetic anisotropy. By tuning incident photon energy to Co 2p&rarr3d transition edge we collected small angle magnetic scattering patterns by a charged coupled device in transmission geometry. Each pattern is an unique fingerprint of the corresponding illuminated domain structure. The patterns were analyzed by an angular correlation method. A variety of striking rotational orders were discovered. Their evolution with applied fields was investigated. The sustainabilities of the orders under the room temperature, exchange biased (EB) state, and non-EB state were compared, which suggests that certain orders can be well manipulated under the EB condition. By simulating magnetic resonant scattering from domain patterns obtained by a direct imaging method, we probed the range of emerging orders and finite size effect. Our study provides a novel approach to characterizing magnetic films and potentially can be extended to any system with a complex microstructure. / 2015-07-11