FePt films with the L10 phase have potential applications for magnetic recording and permanent magnets due to its high magnetocrystalline anisotropy energy density. Heat treatment of n multilayer films is one approach to form the L10 FePt phase through a solid state reaction. This thesis has studied the diffusion and reaction of n multilayer films to form the L10 FePt phase and has used this understanding to construct exchange spring magnets. The process-structure-property relations of n multilayer films were systematically examined. The transmission electron microscopy (TEM) study of the annealed multilayers indicates that the Pt layer grows at the expense of Fe during annealing, forming a disordered fcc FePt phase by the interdiffusion of Fe into Pt. This thickening of the fcc Pt layer can be attributed to the higher solubilities of Fe into fcc Pt, as compared to the converse. For the range of film thickness studied, a continuous L10 FePt product layer that then thickens with further annealing is not found. Instead, the initial L10 FePt grains are distributed mainly on the grain boundaries within the fcc FePt layer and at the Fe/Pt interfaces and further transformation of the sample to the ordered L10 FePt phase proceeds coupled with the growth of the initial L10 FePt grains. A comprehensive study of annealed n films is provided concerning the phase fraction, grain size, nucleation/grain density, interdiffusivity, long-range order parameter, and texture, as well as magnetic properties. A method based on hollow cone dark field TEM is introduced to measure the volume fraction, grain size, and density of ordered L10 FePt phase grains in the annealed films, and low-angle X-ray diffraction is used to measure the effective Fe-Pt interdiffusivity. The process-structure-properties relations of two groups of samples with varying substrate temperature and periodicity are reported. The results demonstrate that the processing parameters (substrate temperature, periodicity) have a strong influence on the structure (effective interdiffusivity, L10 phase volume fraction, grain size, and density) and magnetic properties. The correlation of these parameters suggests that the annealed n multilayer films have limited nuclei, and the subsequent growth of L10 phase is very important to the extent of ordered phase formed. A correlation between the grain size of fcc FePt phase, grain size of the L10 FePt phase, the L10 FePt phase fraction, and magnetic properties strongly suggests that the phase transformation of fccL10 is highly dependent on the grain size of the parent fcc FePt phase. A selective phase growth model is proposed to explain the phenomena observed. An investigation of the influence of total film thickness on the phase formation of the L10 FePt phase in n multilayer films and a comparison of this to that of FePt co-deposited alloy films is also conducted. A general trend of greater L10 phase formation in thicker films was observed in both types of films. It was further found that the thickness dependence of the structure and of the magnetic properties in n multilayer films is much stronger than that in FePt alloy films. This is related to the greater chemical energy contained in n films than FePt alloy films, which is helpful for the L10 FePt phase growth. However, the initial nucleation temperature of n multilayers and co-deposited alloy films was found to be similar. An investigation of L10 FePt-based exchange spring magnets is presented based on our understanding of the L10 formation in n multilayer films. It is known that exchange coupling is an interfacial magnetic interaction and it was experimentally shown that this interaction is limited to within several nanometers of the interface. A higher degree of order of the hard phase is shown to increase the length scale slightly. Two approaches can be used to construct the magnets. For samples with composition close to stoichiometric L10 FePt, the achievement of higher energy product is limited by the average saturation magnetization, and therefore, a lower annealing temperature is beneficial to increase the energy product, allowing a larger fraction of disordered phase. For samples with higher Fe concentration, the (BH)max is limited by the low coercivity of annealed sample, and a higher annealing temperature is beneficial to increase the energy product.

Advanced scanning magnetoresistive microscopy (SMRM) — a robust magnetic imaging and probing technique — is presented. It utilizes conventional recording heads of a hard disk drive as sensors. The spatial resolution of modern tunneling magnetoresistive sensors is nowadays comparable with more commonly used magnetic force microscopes. Important advantages of SMRM are the ability to detect pure magnetic signals directly proportional to the out-of-plane magnetic stray field, negligible sensor stray fields, and the ability to apply local bipolar magnetic field pulses up to 10 kOe with bandwidths from DC up to 1 GHz. The performance assessment of this method and corresponding best practices are discussed in the first section of this work. An application example of SMRM, the study on chemically ordered L10 FePt is presented in a second section. A constructed heater unit of SMRM opens the path to investigate temperature-dependent magnetic properties of the medium by recording and imaging at elevated temperatures. L10 FePt is one of the most promising materials to reach limits in storage density of future magnetic recording devices based on heat-assisted magnetic recording (HAMR). In order to be implemented in an actual recording scheme, the medium Curie temperature should be lowered. This will reduce the power requirements, and hence, wear and tear on a heat source — integrated plasmonic antenna. It is expected that the exchange coupling of FePt to thin Fe layers provides high saturation magnetization and elevated Curie temperature of the composite. The addition of Cu allows adjusting the magnetic properties such as perpendicular magnetic anisotropy, coercivity, saturation magnetization, and Curie temperature. This should lead to a lowering of the switching field of the hard magnetic FeCuPt layer and a reduction of thermally induced recording errors. In this regard, the influence of the Fe layer thickness on the switching behavior of the hard layer was investigated, revealing a strong reduction for Fe layer thicknesses larger than the exchange length of Fe. The recording performance of single-layer and bilayer structures was studied by SMRM roll-off curves and histogram methods at temperatures up to 180 °C In the last section of this work, SMRM advantages are demonstrated by various experiments on a two-dimensional magnetic vortex lattice. Magnetic vortex is a peculiar complex magnetization configuration which typically appears in a soft magnetic structured materials. It consists of two coupled sub-systems: the core, where magnetization vector points perpendicular to the structure plane, and the curling magnetization where magnetic flux is rotating in-plane. The unique properties of a magnetic vortex making it an object of a great research and technological interest for spintronic applications in sensorics or data storage. Manipulation of the vortex core as well as the rotation sense by applying a local field pulse is shown. A spatially resolved switching map reveals a significant "write window" where vortex cores can be addressed correctly. Moreover, the external in-plane magnet extension unit allow analyzing the magnetic vortex rotational sense which is extremely practical for magnetic coupling investigations of magnetic coupling phenomena.

This work has been devoted to the study of phase transformations involving chemical ordering and magnetic properties evolution in bulk Fe-Pt alloys composed of nanometer-sized grains. A comprehensive study of phase transformations and ordering in Fe-Pt alloys is performed by a combination of in-situ neutron powder diffraction and thermal analysis. The dependence of ordering processes on the alloy composition and initial microstructure (homogeneous A1 phase or multilayer-type) is established. Through the use of mechanical alloying and subsequent heat treatment it has been possible to achieve the formation of chemically highly ordered L10 FePt and, in the case of the Fe-rich and Pt-rich compositions, L12 Fe3Pt and FePt3 phases, respectively. Whereas in Pt-rich alloys the decoupling effect of the FePt3 phase leads to coercivity improvement, in Fe-rich nanocomposites a peculiar nanometer scale multilayer structure gives rise to remanence enhancement due to large effects of exchange interactions between the crystallites of the phases. The structure, magnetic properties and magnetisation reversal processes of these alloys are investigated. Experimentally observed phenomena are understood on the basis of a simple two-particle interaction model. Neutron diffraction has also been used for the investigation of the magnetic structure of ordered and partially ordered nanocrystalline Fe-Pt alloys. It has been shown that the magnetic moment of Fe atoms in L10-type Fe Pt alloys is sensitive to the compositional order. The results are compared to density functional calculations.

En raison de leur constante d’anisotropie magnétocristalline particulièrement élevée,les nanoparticules de FePt cristallisant dans la phase « chimiquement » ordonnée L10présentent un grand intérêt pour la réalisation de média magnétiques discrets à très hautedensité (>1 Tb/in2) jusqu’à un diamètre limite de 3,5 nm. Nos travaux portent sur la synthèsepar voie chimique (thermolyse) de nanoparticules de FePt-ɣ, calibrées en taille (4 ≤ Ø ≤ 8 nm)et de composition chimique proche de Fe50Pt50. Par la suite, leur transition vers la variété L10est réalisée afin de leur assurer un comportement ferromagnétique fort à 300 K. En dépitd’une composition non homogène en fer au sein de chaque nanoparticule (coeur riche enplatine et surface davantage riche en fer), la phase L10 est obtenue après un recuit sousatmosphère réductrice (Ar/H2 5%) à des températures supérieures à 650°C. Par ailleurs, afinde prévenir la coalescence des nanoparticules lors du recuit, trois méthodes de protectionsdistinctes ont montré leur efficacité : une matrice de NaCl, des écorces de silice amorphe etde MgO cristallisé. Cette dernière méthode de protection a permis, une fois les recuitsréalisés, de redisperser les nanoparticules de FePt-L10 par le biais d’une modification de leursurface par des chaînes de Polyoxyde d’éthylène-thiol (Mn =2000 g.mol-1). Une encremagnétique est obtenue une fois ces nanoparticules mises en solution avec desmacromolécules de copolymères à blocs Polystyrène-b-Polyoxyde d’éthylène. Le dépôt decette encre sur un substrat permet de former, après auto-assemblage supramoléculaire desmacromolécules, un film hybride contenant les nanoparticules ferromagnétiques FePt-L10localisées sélectivement dans les domaines cylindriques de POE. / Nanoparticles made of FePt alloy in a face-centered-tetragonal (fct) structure have agreat interest for the enhancement of data density (> 1 Tbit/in²) in magnetic recordingmedia due to their high magneto-crystalline anisotropy and low critical diameters (3.5 nm).Our works lie in the synthesis of ɣ-FePt nanoparticles controlled in size (4 ≤ Ø ≤ 8 nm) andchemical composition (≈ Fe50Pt50) by thermal decomposition of organometallic precursors.Following ɣ-FePt NPs synthesis, annealing at high temperature is required for a completetransition from fcc to fct structure (L10) that ensure a ferromagnetic behavior at ambient.Despite a non-homogenous chemical composition on each nanoparticles (platinum-rich coreand iron-rich surface), L10 structure has been obtained after annealing under atmosphereAr/H2 (5%), at temperature up to 650°C. To prevent coalescence of FePt NPs duringannealing, tree distinct protection routes have shown their effectiveness: an inert NaClmatrix, an amorphous silica shell or a crystalline MgO shell. This last method shows bestresults in redispersion of L10-FePt nanoparticles after annealing via surface modification ofnanoparticles by PEO-thiol chains (Mn =2000 g.mol-1). A magnetic ink is then formulated inpresence of PS-b-PEO macromolecules. At least, this as-made ink is deposited on a substrateto obtain, after copolymer self-assembly, a hybrid film containing ferromagnetic L10-FePtnanoparticles selectively located into PEO cylindrical domains.

This work has been devoted to the study of phase transformations involving chemical ordering and magnetic properties evolution in bulk Fe-Pt alloys composed of nanometer-sized grains. A comprehensive study of phase transformations and ordering in Fe-Pt alloys is performed by a combination of in-situ neutron powder diffraction and thermal analysis. The dependence of ordering processes on the alloy composition and initial microstructure (homogeneous A1 phase or multilayer-type) is established. Through the use of mechanical alloying and subsequent heat treatment it has been possible to achieve the formation of chemically highly ordered L10 FePt and, in the case of the Fe-rich and Pt-rich compositions, L12 Fe3Pt and FePt3 phases, respectively. Whereas in Pt-rich alloys the decoupling effect of the FePt3 phase leads to coercivity improvement, in Fe-rich nanocomposites a peculiar nanometer scale multilayer structure gives rise to remanence enhancement due to large effects of exchange interactions between the crystallites of the phases. The structure, magnetic properties and magnetisation reversal processes of these alloys are investigated. Experimentally observed phenomena are understood on the basis of a simple two-particle interaction model. Neutron diffraction has also been used for the investigation of the magnetic structure of ordered and partially ordered nanocrystalline Fe-Pt alloys. It has been shown that the magnetic moment of Fe atoms in L10-type Fe Pt alloys is sensitive to the compositional order. The results are compared to density functional calculations.

The large magneto-crystalline anisotropy energy of the L10 phase has pushed the interest to the FePt nanoparticles to get smallest possible not superparamagnetic particles for magnetic data storage media. The DC magnetron sputtering process, in an inert gas atmosphere and subsequently ejection into high vacuum via differential pumping in addition with a newly constructed light furnace, allows us to have a predeposition annealing of FePt nanoparticles. The advantage compared to wet chemical process route is, that we can prevent the growing of particles on a substrate. In order to determine the experimentally hardly accessible temperature of the particles, the thermal history of the particles is rather calculated from the interaction with the light field along the flight path through the light furnace used for the in-flight annealing. The results obtained for the particle temperature are corroborated by experimental findings on the sintering of agglomerated particles and change in magnetic properties due to heating over the L10 stability temperature. The experiments reveal that the effect of the thermal treatment on both the structural and magnetic properties of the FePt nanoparticles strongly depends on the particles’ crystal structure. The magnetic behavior shows a size depending effective uniaxial magnetic anisotropy constant. This behavior is strongly correlated to the structure of the 5 nm to 8 nm L10 FePt particle.:Einleitung 1 Grundlagen 1.1 Eisen-Platin Nanopartikel 1.1.1 Das System Eisen-Platin 1.1.2 Die A1 - L10 Phasenumwandlung 1.1.3 Größeneinflüsse auf Phasenstabilität und strukturelle Allotropie 1.2 Magnetische Eigenschaften 1.2.1 Magnetokristalline Anisotropieenergie 1.2.2 Ummagnetisierungsverhalten nach Stoner-Wohlfarth (SW) 1.2.3 Ummagnetisierungsverhalten mit kubischer Anisotropie 1.2.4 Skalierungseffekte - Superparamagnetismus 1.2.5 Magnetische Wechselwirkungen zwischen Partikeln 1.3 Nanopartikelentstehung und Thermodynamik der Phasenbildung 1.3.1 Nukleation von Nanopartikeln aus der Gasphase 1.3.2 Partikelwachstum 1.4 Definition der Fragestellung 2 Experimentelles und Methoden 2.1 Das Nanopartikel-Depositions-System 2.2 Konstruktion und Aufbau des Lichtofens 2.2.1 Vermessung der Lichtofenleistung 2.2.2 Justage des Lichtofens 2.3 Optische Wärmebehandlung von Nanopartikeln 2.3.1 Wärmeströme 2.3.2 Absorptionsquerschnitt 2.3.3 Dielektrische Funktion 2.3.4 Schwarzkörperstrahlung 2.3.4.1 Beschreibung des Spektrums von Halogenlampen 2.3.4.2 Abstrahlungsleistung von Nanopartikeln 2.4 Berechnung der Partikeltemperatur 2.4.1 Optische Konstanten für L10-FePt Nanopartikel 2.4.2 Strahlungsverhalten freier Partikel 2.4.3 Numerische Berechnung der Partikelgeschwindigkeit 2.4.4 Experimentelle Bestimmung der Wärmekapazität von FePt 2.4.5 Bestimmung der Partikeltemperatur durch iterative Integration 2.4.6 Zusammenfassende Bewertung zum Optischen Heizen 2.5 Charakterisierung mittels TEM- und HRTEM-Analysen 2.5.1 Bestimmung der Größenverteilung 2.5.2 Bestimmung des Agglomerationsgrades 2.5.3 Auswertung der Kristallstruktur mittels HRTEM 2.6 Magnetisierungsmessungen 2.6.1 Magnetische Charakterisierung mittels VSM-Messungen 2.6.2 Messung der Hysterese-Schleife 2.6.3 Remanenzanalyse 3 Sintern von Partikeln 3.1 Optisches Heizen im Flug 3.2 Diskussion 4 Optimierung der Herstellungsparameter anhand HRTEM-Strukturanalyse 4.1 Einzelpartikel 4.1.1 Ungeheizte Einzelpartikel 4.1.2 Geheizte Einzelpartikel 4.2 Partikel-Agglomerate 4.2.1 Ungeheizte Agglomerate 4.2.2 Geheizte Agglomerate mit hohem Targetalter 4.2.3 Geheizte Agglomerate mit geringem Targetalter 4.3 Diskussion 5 Magnetische Eigenschaften geheizter Partikel 5.1 Einfluss der Wärmebehandlung auf die magnetische Hysterese 5.1.1 Überheizen kleiner Partikel 5.1.2 Überheizen großer Partikel 5.2 Magnetisierungsprozess 5.2.1 Messung des Remanenzverhaltens kleiner und großer Partikel 5.2.2 Temperaturabhängigkeit der Schaltfeldverteilung 5.3 Diskussion 6 Korrelation der effektiven Anisotropie mit der Partikelgrößenverteilung 6.1 Bestimmung der effektiven uniaxialen und kubischen Anisotropieverteilung 6.2 Korrelation der Partikelgröße mit der Anisotropie für kleine Partikel 6.3 Korrelation der Partikelgröße mit der Anisotropie für große Partikel 6.4 Diskussion 7 Zusammenfassung Literaturverzeichnis

Im binären Mn-Ga-System wurde für Legierungen mit 55 at.% bis 65 at.% Mangan die Phasenbildung der L10-Phase mit Röntgenbeugung und Differenzialkalorimetrie untersucht. Nach der Herstellung der L10-Phase in allen Legierungen erfolgte eine Untersuchung der intrinsischen magnetischen Eigenschaften. Die Mn55Ga45-Legierung zeigte dabei die höchste Sättigungsmagnetisierung mit µ0Ms = 0,81 T. Für diese Legierung erfolgten deshalb Versuche zur Verbesserung der extrinsischen Eigenschaften. Dazu wurden Pulver gemahlen und die Möglichkeit der Ausrichtung im Magnetfeld untersucht. Dabei konnte ein Texturgrad von 0,45 für Pulver mit einer Partikelgröße kleiner 10 µm erreicht und die Koerzitivfeldstärke um das 7-fache gegenüber der Volumenprobe erhöht werden. Weiterhin konnten die Pulverproben durch Heißkompaktieren bei 400 °C erneut zu einer Volumenprobe gepresst werden. Die dabei erhaltene Probe besitzt eine Koerzitivfeldstärke von 0,16 T und eine leicht reduzierte Sättigungsmagnetisierung auf Grund einer Packungsdichte von 83 %. Im ternären Mn-Al-Ga-System wurden Proben der Sollzusammensetzung Mn55Al45-xGax mit 5,625 < x < 22,5 hergestellt. Für Legierungen mit x >= 11,86 erwies sich eine Wärmebehandlung bei 600°C für 24 Stunden als ausreichend die reine L10-Phase zu erzeugen. Bei den Legierungen mit einem geringeren Ga-Anteil war eine zweistufige Wärmebehandlung notwendig, um ausschließlich L10 zu erhalten. Nach der ersten Wärmebehandlung bei 1100 °C entstand ein Phasengemisch aus gamma2 und L10(epsilon). Letzteres wurde aus der epsilon-Hochtemperaturphase gebildet. Durch die anschließende Wärmebehandlung bei 500 °C für 24 Stunden konnte die verbleibende gamma2-Phase in L10(gamma2) umgewandelt werden. Untersuchungen der lokalen Legierungszusammensetzung ergaben einen geringeren Mn-Anteil der L10(gamma2)-Phase im Vergleich zu L10(epsilon). Die Unterschiede in den zwei L10-Phasen konnten weiterhin durch eine Reflexaufspaltung in den Röntgenbeugungsaufnahmen sowie der Existenz zweier Curie-Temperaturen bestätigt werden. Die gemessenen Sättigungsmagnetisierungen ergaben eine Superposition beider Phasen und einen maximalen Wert von µ0Ms = 0,85 T. Untersuchungen der thermischen Stabilität der L10-Phasen bei 700 °C zeigten, dass die L10(gamma2)-Phase thermisch stabil ist und sich die L10(epsilon)-Phase langsam in beta-Mn und gamma2 zersetzt. Bei der Zersetzung war im Vergleich zum binären Mn-Al-System eine starke Steigerung der thermischen Stabilität durch die Substitution geringer Mengen Galliums zu erkennen. Über die zersetzungsbedingte Reduktion der Magnetisierung konnten Abschätzungen der Zersetzungskinetik getroffen werden.

In this article, we propose an innovative way of delineating local markets based on easily accessible data. We apply this concept to the day care industry and investigate providers' location choices relative to local market characteristics to evaluate the widespread presumption that local markets for child care services are geographically very small. Using a panel of all day care centers for the metropolitan region of Vienna, Austria, for nearly a decade, as well as geographically extremely disaggregated data on the spatial distribution of children under the age of six at the 250m×250m grid cell level, we find that the location of children and day care centers are strongly related, but this relationship diminishes as soon as the distance between a child's place of residence and the day care center's location increases. We conclude that local markets for day care services in metropolitan regions are indeed very small (about 500m or 550 yards).

Les nanoparticules d'alliage FePt, obtenues dans la phase chimiquement ordonnée L10, présentent un fort intérêt pour la réalisation de média magnétiques à très haute densité de stockage (>1 Tb/in2). Cette thèse concerne l'étude des propriétés structurales et magnétiques de telles nanoparticules synthétisées par voie chimique. L'étude détaillée, structurale et magnétique, de particules de FePt (3-4 nm) met en évidence une structure hétérogène en composition : un coeur riche en Pt (Fe30Pt70) et une surface riche en Fe. Cette structure, obtenue pour plusieurs protocoles de synthèse étudiés, est liée à l'influence des ligands (amine et acide oléiques) sur les vitesses d'incorporation du Fe et du Pt. À partir de cette observation, nous avons mis en oeuvre un nouveau ligand en remplacement de l'amine, le pentadécanenitrile. Nous avons ainsi obtenu des particules de composition plus homogène, et également aptes à l'auto-organisation sur des substrats. Les méthodes de synthèse chimique donnent des particules dans la phase chimiquement désordonnée et des recuits à haute température sont nécessaires pour obtenir la phase L10. Malgré, la présence d'une structure coeur-coquille, la phase L10 est obtenue après un recuit sous vide à 650°C, indiquant que le fer de surface est disponible. Ces recuits s'accompagnent systématiquement d'une forte coalescence des particules. Nous avons donc étudié une voie alternative pour obtenir la phase L10 à des températures modérées : l'irradiation par des ions He+. Les premiers résultats, encourageants, indiquent une homogénéisation de la composition après irradiation des particules à température modérée, ainsi qu'un accroissement de leur aimantation.

Many physical properties, for example structural or magnetic, of a material are directly dependent on elemental composition. Tailoring of properties through highly accurate composition control is possible in thin films. This work exemplifies such tailoring. A short review is given of the current status for research in the area of permanent magnets, focusing on rare earth element free alternatives, where FeNi in the L10 phase is a possible candidate. Epitaxial FeNi L10 thin films were successfully synthesized by magnetron sputtering deposition of monoatomic layers of Fe and Ni on HF-etched Si(001) substrates with Cu or Cu100-xNix/Cu buffers. The in-plane lattice parameter aCuNi of the Cu100-xNix buffer layer was tuned by the Ni content. Through matching of aFeNi to aCuNi, the strain state (c/a)FeNi was controlled, where c is the out-of-plane lattice parameter. The 001 reflection indicative of chemical order, as measured by resonant x-ray diffraction, was in most cases split in two peaks due to a composition modulation of Fe and Ni. This chemical disorder contributed to that the uniaxial magnetocrystalline anisotropy energy, KU≈0.35 MJ/m3, was smaller than predicted. In later experiments the composition modulation could partly be compensated for. Remaining discrepancies with respect to predicted KU values were attributed to additional disorder induced by surface roughness of the buffer layer. The interface sharpness between Fe and Ni was explored by producing epitaxial symmetric multilayers with individual layer thicknesses n = 4-48 monolayers (ML). For n ≤ 8 ML the films had pure fcc structure, with antiferromagnetic Fe layers. For n ≥ 8 ML the Fe layers relaxed to bcc structure. A combinatorial sputter chamber, which has the capability to deposit samples with composition and thickness gradients, was assembled. A model for simulation of composition and thickness across large substrates, for the conditions in this chamber, is presented. The model is verified by comparison to experimental data. Some challenges inherent in combinatorial sputtering are discussed, and two experimental studies employing the technique are presented as examples. These investigated magnetic and structural properties of Tb-Co films, with 7-95 at.% Tb, and of amorphous and crystalline ternary gradient Co-Fe-Zr films, respectively.