Multiferroic materials, in which spontaneous orderings (especially magnetic and electrical, in some cases elastic) jointly exist and may mutually interact, are currently in the center of attention in many fields of research due to their high application potential. They are already used in many applications, as in various sensors, microwave filters or electro / magneto- mechanical manipulators and actuators. Nevertheless, many features of microstructure and moment arrangements are not yet fully explained and understood. The presented work is mostly experimental and focuses on the investigation of several promising multiferroic materials: Pb1 − xBax(Fe0.5Nb0.5)O3 (x = 0 - 1) and Pb(Fe0.5Sb0.5)O3 with a perovskite structure and labeled as multiferroics of the I. type according to the Khomsky classification, BaYFeO4, which belongs to the multiferroics of the II. Khomsky class, and LiFePO4, which is a potentially multiferroic substance containing Fe2+ and are used in electric accumulators at present. Mössbauer spectroscopy of the 57 Fe isotope was used as a key experimental method, which can provide new information about the local arrangement in the vicinity of resonantly absorbing nuclei in the investigated substances. Data evaluation and interpretation would not be possible without the using results...

This dissertation is focused on ferromagnetic, multiferroics, and two-dimensional (2D) perovskites, exploring different unique collective magnetic and ferroic characters: (1) ferromagnetic thin film Co/Pd multilayers, (2) BaTiO3-BiFeO3 (BTO-BFO) a magneto-electric materials system, and (3) CuCl4 halide organic-inorganic perovskites. Low-power all-optical memory offers a unique opportunity to achieve ultra-fast magnetic switching in which the switching dynamics are not thermally mediated and occur on the order of the laser pulse. However, it is challenging to achieve a low-power optically excited magnetization precession angle above 90 degrees, which is required for magnetic switching. Co/Pd thin film multilayers were investigated for their potentially large perpendicular magnetic anisotropy (PMA) with three differing regimes of magnetic anisotropy: in-plane, weakly out-of-plane, and out-of-plane. Utilizing the time-resolved magneto-optical Kerr effect (TR-MOKE), we observed clear magnetic precession (on the order of a few GHz) with magnetic precession angle increasing (up to 4.5 degrees) for thinner Co samples which demonstrated stronger PMA. We observed a clear connection between PMA strength and precession amplitude as well as a large efficiency of energy transfer between spin and orbital subsystems for our strongest PMA sample. BTO-BFO is a strong room-temperature multiferroic with enhanced magneto-electric properties compared to BFO. We utilized time-resolved differential reflectivity (TR-DR) and TR-MOKE to observe strong coherent acoustic phonons in thin films as well as nanorods. Our nanorods showed additional modes (a new 20 GHz and 6 GHz mode) not observed in thin films including the fast 33 GHz mode which showed some weak tunability with high magnetic fields (up to 10 T). The observed tunability of these modes in an external magnetic field shows interesting coupling between magnetic moment and phononic modes which may be caused by the breaking of the spin-cycloid at the interface of the nanorods and the surface of the nanorods. We also observed second harmonic generation (SHG) emission which demonstrated a large enhancement in our nanorod structures with further observation of wavelength dependence. Finally, ferromagnetic resonance on our nanorod and thin film BTO-BFO structures indicated very weak Gilbert damping (on the order of 10−3), demonstrating the practicality of our structure for low-spin loss applications. Lastly, this dissertation focuses on a project around CuCl4 and CuCl2Br2 perovskites in which we observed time-dependent SHG. An increase in SHG as a function of infrared laser exposure is shown to coincide with changes in the crystal structure of the Cu perovskite materials. This increase in SHG was shown to last for a few days after hours of laser exposure indicating a slow hysteretic change to the crystal structure of the perovskites. / Doctor of Philosophy / Multifunctionality in materials is important for various applications including future mem- ory devices where ferromagnetism (collective magnetic order), ferroelectricity (collective electric polarization order), and piezoelectricity (collective strain order) can be implemented in a given device. This dissertation centers on three material systems for exploring ferroic orders: Co/Pd thin multilayers, BaTiO3-BiFeO3 (BTO-BFO) films and nano-rod arrays, and Cu halide organic-inorganic perovskite thin films and 2D structures. Co/Pd thin films demonstrate interesting ferromagnetic order with magnetic anisotropy in which the magnetization of the thin film has a preferred direction based on the thickness of the thin film. BTO-BFO demonstrates coupling between ferroelectric and antiferromagnetic order. The magnetic information may be controlled by applying electric fields or strain and Cu halide perovskites demonstrate potentially created ferroelectric order under long-term laser expo- sure with high ferroelectric switching speeds. Dynamics and nonlinear optical responses in these materials systems were explored with Ti:Sapphire pulsed lasers (∼ 100 fs). Our techniques allowed us for a better understanding of fast carrier and spin dynamics after optical excitation. Furthermore, nonlinear optics, in which two or more photons can be used to emit higher energy photons, were employed to explore the ferroelectric properties within these material systems. The results presented in this dissertation provided information on collective orders and fundamental interactions in several less-explored material systems.

In this thesis results of x-ray scattering and neutron scattering experiments on several strongly correlated transition metal oxides are presented. The prototypical charge ordered cuprate La1.48Nd0.4Sr0.12CuO4 was investigated using polarised neutron scattering. The results show that several proposed schemes for the magnetic order in this class of materials may be ruled out, however the data are consistent with one-dimensional stripe-like magnetic order. X-ray diffraction was used to show that the charge order is insensitive to an applied magnetic field, but might be affected by the existence of superconductivity. The magnetic excitations were also studied, and at low energies a gap in the magnetic fluctuations was observed and there is tentative evidence that this is related to magnetic anisotropy. The spin state transition in LaCoO3 was investigated using neutron inelastic scattering, and excitations reminiscent of those observed in ferromagnets above their critical temperatures were observed. The debate surrounding the nature of the excited spin state, S=1 or S=2, could not be resolved, however. The nature of the spin excitations in La0.82Sr0.18CoO3 was investigated using polarised neutrons and it was found that at low energies the excitations take the form of spin-waves. At higher energies this mode becomes heavily damped, and several possible damping mechanisms for this are discussed. Finally, the multiferroic material DyMn2O5 was studied using x-ray resonant scattering. A complex, temperature dependent, magnetic structure was found using a Dy resonance, which reflects an underlying order of the Mn ions. The measurements were in agreement with a theory of multiferroics based on acentric spin-density waves.

In recent years, there has been an intense interest in understanding the microscopic mechanism of laser induced ultrafast magnetization dynamics in picosecond time scales. Magnetization switching on such a time scale has potential to be a significant boost for the data storage industry. It is expected that the writing process will become ~1000 times faster by this technology, compared to existing techniques. Understanding the microscopic mechanisms and controlling the magnetization in such a time scale is of paramount importance at present. In this thesis, laser induced ultrafast magnetization dynamics has been studied for Fe, Co, GdFe, CoMn and Heusler alloys. A multiscale approach has been used, i.e., first-principles density functional theory combined with atomistic spin dynamics utilizing the Landau –Lifshitz-Gilbert equation, along with a three-temperature phenomenological model to obtain the spin temperature. Special attention has been paid to the calculations of exchange interaction and Gilbert damping parameters. These parameters play a crucial role in determining the ultrafast magnetization dynamics under laser fluence of the considered materials. The role of longitudinal and transversal excitations was studied for elemental ferromagnets, such as Fe and Co. A variety of complex temporal behavior of the magnetic properties was observed, which can be understood from the interplay between electron, spin, and lattice subsystems. The very intricate structural and magnetic nature of amorphous Gd-Fe alloys for a wide range of Gd and Fe atomic concentrations at the nanoscale was studied. We have shown that the ultrafast thermal switching process can happen above the compensation temperature in GdFe alloys. It is demonstrated that the exchange frustration via Dzyaloshinskii-Moriya interaction between the atomic Gd moments, in Gd rich area of these alloys, leads to Gd demagnetization faster than the Fe sublattice. In addition, we show that Co is a perfect Heisenberg system. Both Co and CoMn alloys have been investigated with respect to ultrafast magnetization dynamics. Also, it is predicted that ultrafast switching process can happen in the Heulser alloys when they are doped with heavy elements. Finally, we studied multiferroic CoCr2O4 and Ca3CoMnO4 systems by using the multiscale approach to study magnetization dynamics. In summary, our approach is able to capture crucial details of ultrafast magnetization dynamics in technologically important materials.

No description available.

Le contrôle de la polarisation et de l’aimantation par le biais de champs magnétiques et électriques respectifs font des systèmes magnétoélectriques des candidats prometteurs à de nombreuses applications, parmi lesquelles les dispositifs micro-ondes, les dispositifs de stockage de données à haute densité, etc. L’élaboration d’hétérostructures toujours plus innovantes reste un défi majeur dans le but d’optimiser les densités d’interfaces entre les phases ferroélectriques et ferromagnétiques,et ainsi promouvoir les interactions de couplage mécaniques. Au cours de ce projet de thèse, deux stratégies sont mises en oeuvre pour la conception des matériaux : i) une structure coeur-écorce de type (1-1) composée de nanofils ferromagnétiques (1) dans des nanotubes ferroélectriques (1) àl’intérieur d’une membrane nanoporeuse tridimensionnelle auto supportée etii) une structure en couche mince de type (1-3) constituée de nanofils ferromagnétiques (1) supportés sur un substrat rigide et encapsulés dans une matrice ferroélectrique (3). / Controlling polarization or magnetization by an applied magneticand electric field respectively make magnetoelectric systems promisingcandidates for applications in microwave devices, high density data storagedevices, etc. Designing innovative magnetoelectric heterostructures is thus achallenge to optimize interface density between both ferroelectric andferromagnetic phases, and promote mechanical coupling interactions. In thisthesis project, two strategies are followed for material design: i) 1-1 coreshellstructure with ferromagnetic nanowires (1) inside ferroelectricnanotubes in a self-supported tridimensionnal porous template (1) and ii) 1-3structure where ferromagnetic nanowires (1) are supported on a substrateand embedded in a ferroelectric matrix (3).

Submitted by Maria Aparecida (cidazen@gmail.com) on 2017-05-04T12:27:14Z No. of bitstreams: 1 Barbosa_tese_2015_final.pdf: 18085491 bytes, checksum: fb88b27cf57a9ae236af7360496e03f5 (MD5) / Made available in DSpace on 2017-05-04T12:27:14Z (GMT). No. of bitstreams: 1 Barbosa_tese_2015_final.pdf: 18085491 bytes, checksum: fb88b27cf57a9ae236af7360496e03f5 (MD5) Previous issue date: 2015-12-10 / CAPES, FAPEMA,CNPQ / Multiferroics show coupling between at least two ferroics orders . The rare-earth manganites double perovskite structure are multiferroic materials which have been extensively studied in the last decade since the discovery of the magno capacitance La2NiMnO6 (LNMO). Besides the search for a semiconductor ferromagnetic at room temperature has attracted much attention due to its direct application in Spintronics for development of quantum computers. The LNMO is a semiconductor whose multiferroic ferromagnetic Curie temperature is near room temperature (Tc ~ 280 K), which allows its application in magnetic devices that can be controlled by electric fields. In this work, the dopamos LNMO with different concentrations of barium to investigate the effects on the structural, magnetic and vibrational. The results show that even a small concentration of barium increases the magnetic response due to an increase in structural order and changes the symmetry of LNMO, while the Curie temperature and oxidation states are not changed. Using the results of spin-phonon coupling and infrared spectroscopy we concluded that the structural planning is responsible for increasing the magnetic moment and that the colossal dielectric constant of LNMO is purely extrinsic origin. / Materiais multiferróicos mostram acoplamento entre pelo menos duas ordens ferróicas. As manganitas de terras-raras com estrutura de perovskita dupla são materiais multiferróicos que têm sido extensivamente estudados na última década, desde a descoberta da magnetocapacitância na La2NiMnO6 (LNMO). Ademais a busca por um semicondutor ferromagnético à temperatura ambiente tem atraído muita atenção devido às suas aplicações diretas em Spintrônica para desenvolvimento de computadores quânticos. A LNMO é um multiferróico semicondutor ferromagnético cuja temperatura de Curie é perto da temperatura ambiente (Tc~280 K), o que permite sua aplicação em dispositivos magnéticos que podem ser controlados por campos elétricos. Neste trabalho, dopamos a LNMO com diferentes concentrações de bário para investigar os efeitos nas propriedades estruturais, magnéticas e vibracionais. Os resultados mostram que mesmo uma pequena concentração de bário aumenta a resposta magnética devido ao aumento do ordenamento estrutural bem como muda a simetria da LNMO, enquanto que a temperatura de Curie e os estados de oxidação não são alterados. Usando os resultados do acoplamento spin-fônon e da espectroscopia no infravermelho pudemos concluir que o ordenamento estrutural é responsável pelo aumento do momento magnético e que a constante dielétrica colossal da LNMO tem origem puramente extrínseca.

A particularly interesting class of modern materials is ferroic ceramics. Their characteristic order parameter is a result of quantum chemistry taking place on a sub-Å length scale and long-range couplings, e.g. mediated by electrostatic or stress fields. Furthermore, the particular subclass of multiferroics possesses more than one order parameter and exhibits an intriguing coupling between them, which is interesting both from the fundamental physics point of view as well as from a technological vantage point. While on a more fundamental level it is desirable to elucidate the physical details of the coupling mechanism, this knowledge could subsequently lead to new and technologically interesting multiferroic materials, which overcome their current drawback that only one of the multiple order parameters is appreciably large while the others stay small. Due to the short and long range nature of the driving forces, one challenge for thoroughly understanding ferroic ceramics is the characterization of material properties within a large interval of length scales from several tens of µm to sub-Å. To that end, it is useful to exploit that all order parameters can be described as macroscopic fields, e.g. electric polarization or strain, which, in turn, can be either directly or indirectly probed with an electron beam such as used in Transmission Electron Microscopy (TEM). Consequently, TEM is excellently suited for investigating ferroic materials, i.e., state-of-the-art instruments facilitate aberration corrected imaging within a large magnification interval covering the length scales of interest, in particular the atomic regime. A general drawback of conventional TEM techniques is the loss of phase information originally contained in the scattered electron wave introduced by recording only the electron density. Electron Holography is an advanced TEM technique that facilitates the complete evaluation of the complex electron wave, which, in combination with the manifold possibilities of TEM, provides rather straightforward access to static electromagnetic fields within the ceramic. Nevertheless, quantification of order parameters such as the electric polarization or minute details in electromagnetic fields still require to correlate the experimentally gained observations to physical models, which combine the details of the microscopic imaging process, the electron-specimen scattering, and solid state physics of the specimen. The goal of this work is to investigate and advance the limits of Electron Holography as a truly quantitative TEM technique and apply the findings in, e.g., the investigation of ferroic ceramics. In the light of the previously mentioned difficulties, the problem has to be tackled from different directions: Firstly, the whole holographic imaging process is reviewed and extended, if necessary, in order to provide quantitative measures for systematic and statistical errors inherent to reconstructed waves. In the course of that process, two previously not recognized holography-specific aberrations are identified, firstly, a resolution limiting spatial envelope and secondly, a spatial distortion to the reconstructed wave. Furthermore, several correction strategies have been developed, in order to correct the aforementioned two and other well-known disturbances, e.g. Fresnel fringes from the biprism filament. The previous holographic noise model has been extended to incorporate the important contribution from the detector and consequently to provide realistic statistic error bars of the holographically reconstructed amplitude and phase. Secondly, an investigation of the electron-specimen scattering process itself is conducted, leading to a density matrix description of the holographic measurement. The general laws of quantum electrodynamics provide the framework of that description. Relativistic phenomena such as retardation of electromagnetic fields exchanged between beam electron and specimen and spin-orbit coupling of the beam electron are quantified, where the latter is found to be negligible within TEM. The decoherence of the electron wave by statistical coupling to the thermally moving crystal lattice of ceramics is treated by a newly developed algorithm facilitating in particular the accurate quantification of elastic scattering on heavy elements. Inelastic excitations in the ceramic, e.g. bulk plasmons or core electrons, are treated in combination with elastic scattering to identify their role in the holographic reconstruction process and to develop methods for an accurate calculation. A new scattering algorithm combining elastic and inelastic scattering is developed and applied to predict peculiar scattering contrasts of dipole transitions and to discuss the long-standing problem of contrast mismatch between scattering simulations and conventional imaging. To provide a user-friendly and continuing use of the findings, a software package SEMI (Simulation of Electron Microscopy Imaging) has been written, which facilitates the simulation of elastic and inelastic scattering processes and the subsequent imaging within different approximations, incorporating the newly developed algorithms. Thirdly, Density Function Theory (DFT) solid state calculations have been employed to identify and quantify structural modifications and characteristic electromagnetic fields, such as occurring at domain boundaries, within typical ferroic ceramics like BaTiO3 or BiFeO3, and concomitantly provide models correlating observables of the (holographic) experiment to characteristics of the materials, e.g. the order parameters. This is particularly important when static electromagnetic fields provide no direct information about the order parameter, e.g. the electric polarization, i.e., it is possible to correlate the measurable atomic positions to the electric polarization within linear response theory. A software package ATA (AuTomated Atomic contrast fitting) has been developed facilitating an automated fitting of atomic positions and a subsequent determination of local polarization. In a fourth step, electron holographic experiments analyzed with the help of the revised imaging process in combination with the knowledge gained from scattering theory are used as an input to the models established from solid state physics to yield quantitative information about bulk ferroelectric materials such as BaTiO3 and PbTiO3 and more complicated configurations such as domain walls in BiFeO3 and KnbO3. It is found that particular atomic shifts characteristic for ferroelectrics provide the most reliable quantitative information about the polarization down to nm length scales, whereas minute wave modification due to characteristic electron distributions within the ceramic are currently insufficiently quantitatively interpretable within Electron Holography. The linear response program, correlating atomic positions to ferroelectric polarization with the help of ab-initio calculated Born effective charges, has been successfully applied to determine finite size effects, screening layer widths and polarization charges in non-ferroelectric/ferroelectric layered systems. Finally, a special section considers the evaluation of 3D electromagnetic fields by Electron Holographic Tomography, which provides the means to characterize even more complex 3D domain wall configurations. As the capabilities of the technique are still limited by holographic reconstruction errors and particular tomographic issues such as incomplete projection data, the main focus of that section is put on the characterization and improvement of the tomographic reconstruction process. A Singular Value based reconstruction method is developed, which facilitates a quantification and control of the tomographic reconstruction error. Furthermore, vector field reconstruction is extended in order to treat magnetic vector fields leaking out from the reconstruction volume. / Ferroische Keramiken bilden eine besonders interessante Klasse moderner funktionaler Werkstoffe. Ihr charakteristischer Ordnungsparameter ist das Ergebnis quantenchemischer Prozesse innerhalb einer sub- Å Längenskala und spezifischer langreichweitiger Kopplungen, welche beispielsweise durch elektromagnetische oder Spannungsfelder vermittelt werden. Des Weiteren besitzt die besondere Unterklasse der Multiferroika mehr als einen Ordnungsparameter und zeigt eine faszinierende Kopplung zwischen ihnen, was sowohl vom Standpunkt physikalischer Grundlagenforschung als auch aus technologischer Sicht von Interesse ist. Während es vom fundamentalen Standpunkt erstrebenswert ist, die physikalischen Details des Kopplungsmechanismus aufzuklären, könnte in der Folge dieses Wissen zu neuen und technologisch interessanten multiferroischen Materialien führen, welche den derzeit bestehenden Nachteil, dass nur ein Ordnungsparameter genügend groß ist, während die jeweils anderen klein bleiben, hinter sich lassen. Aufgrund der kurz- und langreichweitigen Natur der Antriebskräfte besteht eine Herausforderung für das umfassende Verständnis ferroischer Keramiken aus der Charakterisierung von Materialeigenschaften innerhalb eines breiten Intervalls von Längenskalen, welches von einigen 10 µm bis unterhalb eines Å reicht. Um dieses Ziel zu erreichen ist es zweckmäßig auszunutzen, dass alle Ordnungsparameter als makroskopische, beispielsweise elektrostatische oder Verzerrungs-, Felder beschrieben werden können, welche wiederum direkt oder indirekt mit einem Elektronenstrahl, wie er im Transmissionselektronenmikrokop (TEM) zur Anwendung kommt, gemessen werden können. Folglich ist die Transmissionselektronenmikroskopie hervorragend geeignet um ferroische Materialien zu untersuchen, das heißt, modernste Geräte ermöglichen aberrationskorrigierte Aufnahmen innerhalb eines großen Vergrößerungsbereiches, welche die interessanten Längenskalen und insbesondere den atomaren Bereich abdecken. Ein allgemeiner Nachteil der konventionellen TEM Techniken ist der Verlust der Phaseninformationen, welche ursprünglich in der Elektronenwelle vorhanden sind und durch die Aufzeichnung der Elektronenintensität zerstört werden. Elektronenholographie ist eine weiterentwickelte TEM Technik, welche die vollständige Auswertung der komplexen Elektronenwelle ermöglicht, was wiederum in Verbindung mit den vielfältigen Möglichkeiten der TEM einen vergleichsweise direkten Zugang zu elektromagnetischen Feldern in der Keramik ermöglicht. Nichtsdestotrotz erfordert die Quantifizierung von Ordnungsparametern, wie der elektrische Polarisierung, oder von kleinsten Details elektromagnetischer Felder die Korrelation experimenteller Daten mit physikalischen Modellen, welche die Details des mikroskopischen Bildgebungsprozesses mit der Elektronen-Objekt Streuung und der Festkörperphysik des Objektes kombinieren. Das Ziel dieser Arbeit besteht aus der Untersuchung und Erweiterung der Möglichkeiten von Elektronenholographie als quantitative TEM Messmethode und der Anwendung dieser Ergebnisse bei der Untersuchung ferroischer Keramiken. Im Lichte der eben erwähnten Schwierigkeiten muss das Problem von verschiedenen Richtungen bearbeitet werden: Erstens wird der komplette holographische Bildgebungsprozess mit dem Ziel einer quantitativen Bewertung systematischer und statistischer Fehler der rekonstruierten Welle analysiert und gegebenenfalls erweitert. Im diesem Zuge wurden zwei bisher nicht erkannte holographiespezifische Fehler identifiziert, erstens eine auflösungsbegrenzende räumliche Enveloppe und zweitens eine räumliche Verzerrung der rekonstruierten Welle. Außerdem wurden verschiedene Korrekturmöglichkeiten entwickelt, um die zwei eben genannten und andere wohlbekannte Störungen, wie zum Beispiel die Fresnelstreifen des Biprismafadens, zu korrigieren. Das bisherige holographische Rauschmodel wurde erweitert um den beträchtlichen Einfluss des Detektors zu berücksichtigen und damit realistische Fehlerbalken für die holographisch rekonstruierte Amplitude und Phase zu erhalten. Zum Zweiten wird der Streuprozess selber untersucht, was zu einer Dichtematrixbeschreibung der holographischen Messung führt. Den Rahmen dieser Untersuchungen liefern die Gesetze der Quantenelektrodynamik. Relativistische Phänomene wie die Retardierung elektromagnetischer Felder, welche zwischen Strahlelektron und Objekt ausgetauscht werden, oder Spin-Bahn Kopplung des Strahlelektrons werden quantifiziert, wobei letzteres als unwichtig für TEM eingestuft werden konnte. Die Dekohärenz der Elektronenwelle durch die statistische Kopplung an das thermisch bewegte Kristallgitter der Keramik wird mit einem neu entwickelten Algorithmus beschrieben, welcher insbesondere die genaue Quantifizierung der elastischen Streuung an schweren Elementen erlaubt. Ein weiterer neuer Streualgorithmus, welcher elastische und inelastische Streuung kombiniert, wird entwickelt und angewendet, um spezifische Streukontraste von Dipolübergängen vorauszusagen und das altbekannte Problem der Kontrastdiskrepanz zwischen simulierten und experimentellen Bildkontrasten zu diskutieren. Um eine anwenderfreundliche und fortdauernde Anwendung der Erkenntnisse zu ermöglichen, wurde das Softwarepaket SEMI geschrieben, welches die Simulation elastischer und inelastischer Streuprozesse und des nachfolgenden Bildgebungsprozesses innerhalb verschiedener Näherungen ermöglicht und die neu entwickelten Algorithmen beinhaltet. Zum Dritten kommen dichtefunktionalbasierte Festkörperrechenmethoden zur Anwendung um charakteristische elektromagnetische Felder, wie sie beispielsweise an Domänengrenzen entstehen, innerhalb typischer ferroischer Keramiken wie BaTiO3 oder BiFeO3 zu identifizieren und zu quantifizieren und gleichzeitig Modelle zu entwickeln, welche Observablen des (holographischen) Experiments mit Charakteristika des Materials, beispielsweise den Ordnungsparamtern, korrelieren. Dies ist besonders wichtig, wenn statische elektromagnetische Felder keinen direkten Zugang zu den Ordnungsparametern, wie zum Beispiel die ferroelektrische Polarisation, liefern; beispielsweise besteht innerhalb linearer Antworttheorie die Möglichkeit, atomare Positionen mit der elektrischen Polarisation zu korrelieren. Ein Softwarepaket wurde entwickelt, welches die automatische Bestimmung der Atompositionen und der daraus resultierenden lokalen Polarisation ermöglicht. In einem vierten Schritt wurden mit Hilfe des überarbeiteten holographischen Bildgebungsprozesses in Kombination mit den aus der Streutheorie gewonnenen Erkenntnissen holographische Experimente analysiert und als Input für die mit Hilfe der Festkörpertheorie entwickelten Modelle genutzt, um quantitative Informationen über raumferroische Materialien wie BaTiO3 und PbTiO3 und kompliziertere Anordnungen wie Domänengrenzen in BiFeO3 und KnbO3 zu gewinnen. Es konnte festgestellt werden, dass spezifische atomare Verschiebungen, welche charakteristisch für Ferroelektrika sind, die zuverlässigste quantitative Information über die Polarisation bis in den Längenbereich einiger nm liefern, wogegen kleinste Wellenmodifikationen aufgrund charakteristischer Elektronenverteilungen innerhalb der Keramik mit Hilfe von Elektronenholographie nur unzureichend interpretierbar sind. Das lineare Antwortprogramm, welches die Atompositionen über Bornsche effektive Ladungen mit ferroelektrischer Polarisation korreliert, wurde erfolgreich angewendet, um Größeneffekte und Ausdehnungen von Abschirmschichten und Polarisationladungen in nichtferroelektrisch/ferroelektrischen Schichtsystemen zu bestimmen. Abschließend widmet sich ein spezieller Abschnitt der Auswertung 3D elektromagnetischer Felder mit Hilfe der elektronenholographischen Tomographie, was die Voraussetzung für die Charakterisierung von noch komplizierteren 3D Domänenwandanordnungen liefert. Da die Möglichkeiten dieser Technik durch den holographischen Rekonstruktionsfehler und spezifisch tomographische Probleme noch beschränkt sind, liegt der Schwerpunkt dieses Abschnitts in der Charakterisierung und Verbesserung des tomographischen Rekonstruktionsprozesses. Es wird eine singulärwertbasierte Rekonstruktionsmethode entwickelt, welche die Quantifizierung und Kontrolle des Rekonstruktionsfehlers ermöglicht. Außerdem wird die Vektorfeldrekonstruktion erweitert, um magnetische Vektorfelder, welche über das Rekonstruktionsvolumen hinausragen, zu behandeln.

Ces dernières années, les performances des matériaux multiferroïques ont beaucoup progressé avec les composites à deux phases : magnetostrictive et piézoélectrique. Les composites utilisent le couplage entre le magnétisme et la piézoélectricité par le biais de la magnétostriction. On obtient ainsi le contrôle de l’aimantation par le champ électrique électrique et à l’inverse celui de la polarisation électrique par un champ magnétique (ce qui nous intéresse ici). Cela pousse l’électronique vers des solutions plus vertueuses pour l’environnement avec une baisse de la consommation électrique des circuits (les commandes en courant sont remplacées par des commandes en tension) et le remplacement des piles d’alimentation, qui doivent être changées périodiquement, par des systèmes de récupération d’énergie pérenne. La récupération d’énergie est très présente avec l’Internet des Objets (IoT). Malgré leur performance, ces composites restent perfectibles, notamment au niveau de la phase magnetostrictive. Son optimisation est indispensable. Le matériau courant est le Terfenol-D à cause de sa magnétostriction géante, dans sa forme massive et monocristalline. Ce matériau historique demeure rare, cher, fragile et son procédé de tirage n’est pas adapté à la fabrication de dispositifs miniatures. Ce travail a donc porté sur l’étude comparative des voies de fabrication de disques miniatures de Terfenol-D pour la réalisation de récupérateurs d’énergie. Une étude de fond a été menée sur des séries de disques découpés dans des lingots d’alliages commerciaux (monocristallins et polycristallins). Ensuite, nous sommes tournés vers la méthode du frittage isotrope de poudre avec très peu de recul sur ce matériau. Le frittage conventionnel a conduit aux premiers disques fonctionnels sans découpe mais manquant de densité et de tenue mécanique. Ces défauts ont ensuite été corrigés grâce à la technique de SPS (Spark Plasma Sintering) mais la reproductibilité dans le temps reste à améliorer. Les disques de Terfenol-D (découpés et fabriqués) ont été assemblés avec la phase piézoélectrique (PZT commercial). Des caractérisations électriques par la méthode sans contact ont validé leur aptitude à récupérer de l’énergie, en proportion moindre quand on le compare au Terfenol-D monocristallin comme attendu, mais en quantité suffisante pour les applications ciblées. Enfin, une solution alternative a été explorée avec l’alliage magnétique à mémoire de forme NiMnGa offrant de très grandes déformations. Une perspective vers un bouton poussoir autonome sans fil est présentée en toute fin. / In recent years, performances of multiferroïc materials have considerably improved with two-phase composites: magnetostrictive and piezoelectric. These composites take advantage of the coupling between magnetism and piezoelectricity through magnetostriction. Thus they allow control of magnetization with electrical voltage, and conversely, to get an electrical polarization depending on the magnetic field (our focus in this case). This drives electronics towards more environmental friendly solutions, namely with lower circuit power consumption (current controls are replaced by voltage controls) and the replacement of batteries, which must be periodically changed, by sustainable energy harvesting systems. Energy harvesting solutions are popular with the Internet of Things (IoT). Despite their performance, these multiferroïc composites remain perfectible, especially regarding the magnetostrictive phase. Its optimization is essential. The common material is Terfenol-D because of its giant magnetostriction, used in its massive and monocrystalline form. This material remains rare, expensive, fragile and its growing method is not adapted to the manufacturing of miniature devices. This work focuses on a comparative study of Terfenol-D miniature disk manufacturing pathways for the production of energy harvesters. A benchmark study was carried out on a series of disks cut in commercial alloy ingots (monocrystalline and polycrystalline). Next, the isotropic powder sintering method was investigated with very little background on this material. Conventional sintering led to the first functional disks needing no ulterior machining but with low density and mechanical strength. These defects were then corrected using the SPS technique (Spark Plasma Sintering) but the reproducibility over time has yet to be improved. The Terfenol-D disks (both cut and manufactured) were assembled with the piezoelectric phase (commercial PZT). Electrical characterizations using a contactless method have validated their potential to harvest energy, in lesser amounts than monocrystalline Terfenol-D as expected, but in a large enough quantity regarding most of applications. Finally, an alternative solution has been explored with NiMnGa shape magnetic alloys offering very large deformations. A perspective to a wireless autonomous push button prototype is presented at the very end.

Title: Local structure of hexagonal ferrites studied by NMR Author: Karel Kouřil Department/Institute: Department of Low Temperature Physics Supervisor of the doctoral thesis: prof. RNDr. Helena Štěpánková, CSc. Abstract: Hexagonal ferrites of M, W, X and Y structure types were studied by means of NMR, electronic structure calculations and magnetoelectric experi- ments. Presented results deal with cation distribution, localization of ferrous ions, interpretation of NMR spectra of studied materials and effects of size reduction. In oriented layers M type strontium ferrite and submicron particles of M type barium ferrite pronounced effects of reduced size were observed on 57 Fe NMR spectra. Performance of magnetoelectric barium-strontium Y type hexaferrites with divalent zinc cations improved upon thermal treatment of samples while distribution of zinc was not significantly altered. In Sc sub- stituted BaM, Sc content was found to be uniform throughout TSSG grown crystal. In LaSrM systems electron localization in 2a sublattice was observed, co-substitution with La+Zn, La+Co and La+Cu was found to lead to partial charge compensation. In strontium ferrites of type W and X localization of ferrous ions in octahedral sites in SS block pair was observed. Keywords: NMR, hexagonal ferrites, structure,...