Developing a greater understanding of multiferroic materials, particularly those in which a strong coupling is exhibited between magnetic and electrical orderings, is of great importance if potential applications are to be realised. This thesis reports new experimental findings on several multiferroics using the techniques of X-ray and neutron diffraction together with nonlinear optical experiments. Spherical neutron polarimetry measurements on RbFe(MoO<sub<4</sub>)₂ show how this system's chiral magnetic structure can be controlled by an external electric field. Consideration is given to the axial distortion that the crystal structure makes, and the effect that this has on the stabilised magnetic structures. A ferroaxial coupling is invoked to explain, from a symmetry point of view, the spin driven multiferroicity in this proper screw system. The charge ordering in YbFe₂O₄ is examined by a detailed imaging of reciprocal space measured by elastic X-ray diffraction. Continuous helices of scattering are observed above the three-dimensional ordering transition temperature, whereas the intensity is concentrated onto separated maxima below this. The low temperature data are modelled using a simple oxygen displacement pattern, generalised to an incommensurate structure. The observed incommensurability implies that YbFe₂O₄ cannot be truly ferroelectric. The low field magnetic structures of a Y-type hexaferrite Ba_0.5Sr_1.5Zn₂Fe₁₂O₂₂ are observed in a resonant soft X-ray diffraction study. In zero field the system is helimagnetic, and with small applied fields peaks corresponding to a new phase appear. Energy calculations are used to suggest a suitable magnetic structure for the new phase and to show how this relates to the known commensurate phases that are present in low fields. Finally, an experimental setup designed to measure second harmonic generation from non-centrosymmetric crystals is presented, along with static measurements on the multiferroic system MnWO₄. An optical pump / second harmonic probe study is then undertaken, with the result that a pump induced enhancement in the efficiency of the second harmonic generation is observed.

This thesis presents experimental results on two complex oxide systems: Cu_1-xZn_xO and La_0.7Sr_0.3MnO₃:ZnO. The dynamic magnetoelectric response of these materials is obtained using terahertz time-domain spectroscopy, supported by Fourier-transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction. Evidence for an electromagnon in the multiferroic phase of CuO is presented for the first time. This high temperature (213-230K) electromagnon is linked to intersublattice exchange between two Cu sublattices. The temperature dependence of a magnon in the collinear antiferromagnetic phase is indicative of biquadratic exchange. Broadening of the multiferroic phase on substitution of copper with zinc is reported along with a 25% depression of the Néel temperature due to spin dilution. Phonons and magnons broaden and shift in energy on alloying. However, the electromagnon is relatively insensitive, increasing in energy without widening. This indicates that electromagnons and dynamic magnetoelectric coupling can be mantained even in disordered spin systems. Strong spin-phonon coupling is present in both magnetically ordered phases as shown by the anomalous behavior of the A³<sub style='position: relative; left: -.5em;'>u</sub> phonon at T_N1 and a Raman-active mode associated with a magnetic modulation of a zone-folded acoustic phonon. Dynamic 1THz magnetoresistance is found to be significantly larger than static magnetoresistance in La_0.7Sr_0.3MnO₃:ZnO vertically-aligned nanocolumns on LaAlO₃ substrates. The metal-insulator transition temperature is determined to be 300 K. Temperature dependent static and dynamic resistivity and magnetoresistance are discussed in terms of strain and grain boundary effects. Negative photoconductivity is observed and the dynamic response analysed.

Materiais que apresentam um acoplamento entre as propriedades elétricas e magnéticas, conhecidos como magnetoelétricos, estão despertando a atenção da comunidade acadêmica nos últimos anos principalmente devido ao seu grande potencial tecnológico no desenvolvimento de materiais multifuncionais. Sendo um maior esforço concentrado na obtenção de novos materiais multiferróicos, que são aqueles que possuem duas ou mais ordens ferróicas, em especial os que apresentam ferroeletricidade e ferromagnetismo. Este trabalho tem como objetivo uma investigação das propriedades dielétricas e magnéticas de um grupo de materiais ainda pouco estudado a fim de se compreender os mecanismos responsáveis pelo efeito magnetoelétrico, de forma a contribuir com a pesquisa nessa área. As amostras estudadas são os óxidos de titânio e cromo Nd(1-x)A(x)CrTiO5 (A=Y, La) e GdCrTiO5, todos na forma de cerâmicas policristalinas monofásicas. Foram discutidas de que forma a diluição da subrede magnética do neodímio afeta o caráter magnetoelétrico observado nesse material e qual a importância de cada uma das subredes (Nd3+/Gd3+ e Cr3+) nas propriedades dielétricas e magnéticas. Verificamos que o efeito magnetoelétrico é sensível a variações na rede do Nd3+. Entretanto, nossos resultados no composto GdCrTiO5 indicam que as subredes magnéticas são pouco acopladas, o que indica que o ion Cr3+ talvez seja o responsável por dirigir o efeito magnetoelétrico nesta família de materiais. / The coupling of the electric and magnetic properties in the magnetoelectric compounds is attracting a great deal of interest in the scientific community due to the huge potential for application based on new multifunctional materials. Of special attention are the so-called multiferroics, materials that simultaneously show ferromagnetism and ferroelectricity. The main purpose of this work is the experimental investigation of the dielectric and magnetic properties of a relatively less known class of materials with the aim to identify the origin of the magnetoelectric coupling. We study the single phase polycrystalline compounds Nd(1-x)A(x)CrTiO5 (A=Y, La) and GdCrTiO5 and discuss the effect of dilution of the Nd3+ ions and the importance of each magnetic sublattice on the samples behavior. We find that the magnetoelectric effect is susceptible to changes in the Nd3+ site. At the same time, our results indicate that the two magnetic sublattice (Nd3+/Gd3+ and Cr3+) are only weakly coupled indicating that the Cr3+ magnetic sublattice might be responsible for driving the magnetoelectric effect in this family of compounds.

Magnetic and ferroelectric materials have both had a very important impact in our society, not only because of the fascinating science behind the two phenomena, but also as a result of their use in many technological applications. The coupling and coexistence of these two order parameters within the same material opens the door to exiting new functional devices. Materials where magnetism and ferroelectricity coexist are known as multiferroic materials. In this thesis, muon spectroscopy and other complementary experimental techniques, including neutron scattering and resonant ultrasound spectroscopy, are used to investigate two di↵erent multiferroics. Muon and total neutron scattering studies have been performed on BiFeO3, one of the most studied multiferroic materials. Muon measurements reveal an anomaly in the temperature region of 200 - 220 K with a sudden and abrupt change in the muon’s precession frequency that corresponds to a process of muon di↵usion throughout the entire sample. The pair distribution function, calculated from total neutron scattering experiments on the compound, suggest that a change in the local structure of the material involving the bismuth-oxygen bond, in the same temperature region as the muon di↵usion sets in, is a strong indicative that there is a link between two in terms of the muon di↵usion being triggered by these local changes. Also, an extensive analysis and characterisation of the magnetic and ferroelectric properties of Ba4Dy0.87Nb10O30, an entirely new tetragonal tungsten bronze magnetoelectric material, is given. Neutron scattering and dielectric measurements are used to show that this material becomes ferroelectric below 470 K. We use muon spectroscopy and magnetic susceptibility measurements to investigate the magnetic properties of the material. Muon measurements under an applied electric field indicate that there is a strong coupling between the magnetism and ferroelectricity in the material. Resonant ultrasound spectroscopy is use to investigate whether the source of this coupling could be related to strain e↵ects. Magnetic neutron scattering measurements show that there is no long range ordering in the material.

We studied the pressure effect of polycrystal BiMnO3 (type-I multiferroic) and single crystal Co3TeO6 (type-II multiferroic) with different magnetic fields and pressures. With the primary objective of understanding the pressure effect on BiMnO3, complex multiple magnetic transitions (kink I, II and III) are observed under the maximum applied pressure of 15.94 kbar (~1.6 GPa). Kink I, a long-range soft ferromagnetic transition at TcI ~ 100 K under ambient pressure, is suppressed completely at 11.74 kbar. Kink II emerges at 8.66 kbar along with TcII ~ 93 K. Kink II is a long-range soft ferromagnetic the same as kink I but canted in nature. Kink III, a canted antiferromagnetic transition at TcIII ~ 72.5 K appears along with kink II also at 8.66 kbar. These results indicate the complicated correlation between the lattice distortion and the spin configuration under pressures and magnetic fields in multiferroic system. Whereas, two distinct anomalies (T1 ~ 26 K and T2 ~ 18 K) are observed on single crystal Co3TeO6 in magnetic susceptibility, specific heat, and neutron diffraction measurements. Interestingly, the strong anisotropic magnetic variations are also noticed in high-magnetic-field hysteresis measurements with applied magnetic field parallel to a- and c- axes. Dielectric studies were also carried out in different magnetic fields at the temperature range 5 ¡V 300 K. Concomitantly, frequency-independent step-like dielectric anomaly is observed around 18 K, coinciding with the transition of magnetic susceptibility, specific heat, and neutron diffraction. The dielectric constant is also modified by external magnetic fields. These experimental results strongly suggest the multiferroicity of Co3TeO6. From temperature-dependent X-ray diffraction studies, it is evident that a structural distortion appears around 18 K, responsible of dielectric and/or magnetic ordering. The transition at 18 K is disappeared under pressure above 9.82 kbar, indicative of suppressing structural distortion. Similarly, the lattice distortion and the spin configuration under pressures are important factors for multiferroic property. Through the specific heat and pressure-dependent susceptibility, the structural distortion probably results from the magnetic ordering, indication the dielectric anomaly at 18 K.

Submitted by João Francisco Vieira Masteghin null (joaomasteghin@gmail.com) on 2018-04-16T21:18:21Z No. of bitstreams: 1 Dissertação Final.pdf: 2348816 bytes, checksum: 9fdfdbe5ee57f69406f5ad67e41a18fc (MD5) / Approved for entry into archive by Cristina Alexandra de Godoy null (cristina@adm.feis.unesp.br) on 2018-04-17T13:19:42Z (GMT) No. of bitstreams: 1 masteghin_jfv_me_ilha.pdf: 2348816 bytes, checksum: 9fdfdbe5ee57f69406f5ad67e41a18fc (MD5) / Made available in DSpace on 2018-04-17T13:19:42Z (GMT). No. of bitstreams: 1 masteghin_jfv_me_ilha.pdf: 2348816 bytes, checksum: 9fdfdbe5ee57f69406f5ad67e41a18fc (MD5) Previous issue date: 2018-02-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Foram preparados filmes finos, de Ferrita de Bismuto (BiFeO3), considerado um dos principais multiferróico que são classes de materiais que apresentam ferroeletricidade e ferromagnetismo simultaneamente. Os filmes foram preparados por um rota química chamada de Sol-gel modificado, variando-se a quantidade de % de mol do Bismuto, depositados em substratos de platina Pt/TiO2/SiO2/Si(100), variando-se a temperatura de cristalização entre 400°C a 600°C, com o objetivo de eliminar algumas fases indesejadas encontradas na literatura. Alguns filmes finos passaram pelo tratamento térmico em atmosférica de O2, com o intuito de diminuir a condutividade, causada pelas vacâncias de oxigênio no material. Pelos resultados obtidos foi possível conseguir filmes finos sem as fases indesejadas e com condutividade não tão alta, sendo possível realizar análises elétricas. Assim, tornou-se possível analisar o comportamento da permissividade, impedância e condutividade em função do campo aplicado e da temperatura. Com tais resultados mostra-se a indicação de polarização iônica nestes filmes. Eles apresentam uma energia de ativação parecida com filme finos encontrados na literatura. Além disso, também mostra que o comportamento das propriedades físicas são os mesmos quando varia a temperatura e o campo. / Bismuth Ferrite (BiFeO3) thin films were prepared, considered one of the main multiferroic that are classes of materials that present ferroelectricity and ferromagnetism simultaneously. The films were prepared by a chemical path called modified sol-gel, varying the amount of Bismuth mol percentage, deposited on Pt/TiO2/SiO2/Si(100) platinum substrates, varying the crystallization temperature between 400 °C to 600 °C, with the aim of eliminating some unwanted phases found in literature. Some thin films underwent the thermal treatment in atmospheric O2, in order to reduce the conductivity, caused by the oxygen vacancies in the material. By the results obtained, it was possible to obtain thin films without the undesired phases and with not so high conductivity, being possible to perform electrical analysis. This way it was possible to analyze the behavior of the permissiveness, impedance and conductivity in function of the applied field and temperature. With these results, it is shown an indication of ionic polarization in these films. They have an activation energy similar to thin films found in literature. It is also shown that the behavior of the physical properties are the same when temperature and the field change.

Materiais que apresentam um acoplamento entre as propriedades elétricas e magnéticas, conhecidos como magnetoelétricos, estão despertando a atenção da comunidade acadêmica nos últimos anos principalmente devido ao seu grande potencial tecnológico no desenvolvimento de materiais multifuncionais. Sendo um maior esforço concentrado na obtenção de novos materiais multiferróicos, que são aqueles que possuem duas ou mais ordens ferróicas, em especial os que apresentam ferroeletricidade e ferromagnetismo. Este trabalho tem como objetivo uma investigação das propriedades dielétricas e magnéticas de um grupo de materiais ainda pouco estudado a fim de se compreender os mecanismos responsáveis pelo efeito magnetoelétrico, de forma a contribuir com a pesquisa nessa área. As amostras estudadas são os óxidos de titânio e cromo Nd(1-x)A(x)CrTiO5 (A=Y, La) e GdCrTiO5, todos na forma de cerâmicas policristalinas monofásicas. Foram discutidas de que forma a diluição da subrede magnética do neodímio afeta o caráter magnetoelétrico observado nesse material e qual a importância de cada uma das subredes (Nd3+/Gd3+ e Cr3+) nas propriedades dielétricas e magnéticas. Verificamos que o efeito magnetoelétrico é sensível a variações na rede do Nd3+. Entretanto, nossos resultados no composto GdCrTiO5 indicam que as subredes magnéticas são pouco acopladas, o que indica que o ion Cr3+ talvez seja o responsável por dirigir o efeito magnetoelétrico nesta família de materiais. / The coupling of the electric and magnetic properties in the magnetoelectric compounds is attracting a great deal of interest in the scientific community due to the huge potential for application based on new multifunctional materials. Of special attention are the so-called multiferroics, materials that simultaneously show ferromagnetism and ferroelectricity. The main purpose of this work is the experimental investigation of the dielectric and magnetic properties of a relatively less known class of materials with the aim to identify the origin of the magnetoelectric coupling. We study the single phase polycrystalline compounds Nd(1-x)A(x)CrTiO5 (A=Y, La) and GdCrTiO5 and discuss the effect of dilution of the Nd3+ ions and the importance of each magnetic sublattice on the samples behavior. We find that the magnetoelectric effect is susceptible to changes in the Nd3+ site. At the same time, our results indicate that the two magnetic sublattice (Nd3+/Gd3+ and Cr3+) are only weakly coupled indicating that the Cr3+ magnetic sublattice might be responsible for driving the magnetoelectric effect in this family of compounds.

Indiana University-Purdue University Indianapolis (IUPUI) / Thermal constraints and the quantum limit will soon put a boundary on the scale of new micro and nano magnetoelectronic devices. This necessitates a push into the limits of harnessable natural phenomena to facilitate a post-Moore’s era of design. Requirements for thermodynamic stability at room temperature, fast (Ghz) switching, and low energy cost narrow the list of candidates. Here we show voltage controllable, room temperature, stable locking of the spin state, and the corresponding conductivity change, when molecular spin crossover thin films are deposited on a ferroelectric substrate. This opens the door to the creation of a non-volatile, room temperature, molecular multiferroic gated voltage controlled device.

Les matériaux multiferroïques magnétoélectriques (ME) présentant simultanément des propriétés couplées de ferromagnétisme et de ferroélectricité suscitent beaucoup d’attention, non seulement pour leurs applications (comme la RAM magnétique de nouvelle génération), mais aussi pour la compréhension de la physique relative à ce couplage. Le but de cette thèse était de découvrir et de caractériser de nouveaux composés potentiellement multiferroïques, d’où le choix des trirutiles inverses. Ce manuscrit présente l'étude détaillée du trirutile inverse Mn2TeO6 et quelques résultats sur la série substituée au chrome Mn2-xCrxTeO6. Les composés Mn2TeO6 et substitués sont préparés par réaction à l'état solide à relativement basse température (<700°C). De nombreuses expériences de diffraction de neutrons et de rayons-X ont été réalisées pour étudier les structures cristallines et magnétiques en fonction de la température (de 700°C à 1.5K), ces données ont été analysées en lien avec les caractérisations des propriétés magnétiques et électriques. Mn2TeO6 s’est révélé un matériau complexe et riche en transitions en fonction de la température. En température décroissante, Mn2TeO6 présente d’abord une transition d’une structure tétragonale (P42/mnm) à une double maille monoclinique (P21/c) vers 400°C due à l'effet Jahn-Teller. Une seconde transition très hystérétique apparait à plus basse température, avec la coexistence de deux phases monocliniques entre 45 et 100K. Des transitions magnétiques sont également observées par des mesures de susceptibilité magnétique et de diffraction neutronique. La structure cristalline à température ambiante met en évidence un ordre orbitalaire, dû au manganèse trivalent, complexe et inédit avec une alternance d’octaèdres MnO6 allongés et aplatis décrivant des chevrons. L’impact de l’effet Jahn-Teller induit par le manganèse trivalent est confirmé dans les composés substitués au Cr (avec x ≥ 0,15) qui conservent la structure quadratique sur toute la gamme de température. / Magnetoelectric (ME) multiferroic materials, which present simultaneously two coupled properties between ferromagnetism and ferroelectricity, have attracted much attention recently, not only owing to their application perspectives, e.g., next-generation magnetic RAM, but also for the rich physics associated with the understanding of this coupling. Inverse trirutiles are of particular interest here since ME properties have been reported in this family of compounds. This manuscript presents the study of inverse trirutile Mn2TeO6 and its Cr-substitution series Mn2-xCrxTeO6. Mn2TeO6 and Cr-substituted series were prepared by solid state reaction at relatively low-temperature (< 700°C). Thanks to an extensive use of different techniques performed in a large temperature range (1.5K to 700°C), encompassing synchrotron, neutron and electron diffraction experiments combined with physical properties measurements, the very complex behaviour of Mn2TeO6 was revealed. A structural transition at 400°C from tetragonal (P42/mnm) to monoclinic (P21/c) is observed first, and related to a cooperative Jahn-Teller effect. Further cooling the sample, a hysteretic structural transition is observed spanning more than 50K, which leads to the coexistence of two monoclinic phases. A series of magnetic transitions are also observed between 48K and 22K, with magnetization, heat capacity measurement and neutron diffraction. Cr-substituted (x ≥ 0.15) samples crystallize in the tetragonal phase, implying the suppression of the cooperative Jahn-Teller effect, and involving a simpler, though short–range, magnetic order.

Strain-mediated magnetoelastic composite materials are being considered for communication in lossy environments. Their consideration is attributable to predictions stating order of magnitude improvements over current antenna technology. The magnetic antenna design considered herein consists of three layers: 1) a piezoelectric layer, 2) a linear elastic layer, and 3) a magnetoelastic layer. The antenna operates by mediating strain through the device in a resonant bending mode. The magnetoelastic layer is stressed which results in a changing magnetization ultimately leading to a changing magnetostatic field in free space which acts as a signal for information transfer. In order to prove the efficacy of this approach finite element models have been developed to aid in the design and optimization process. Where these models fall short is in their overall run-time to fully resolve the coupled dynamics. It is for this reason that the work presented in this thesis focuses on the development of a figure of merit capable of predicting optimal bias conditions and geometries needing only the data from a static bias study from FEA. The material level magnetomechanical coupling factor is chosen as the foundation for the figure of merit. The figure of merit is then augmented to include structure level information regarding the demagnetizing field and the non-uniform stress distribution. The main results presented are the effects of including demagnetization and stress distributions, and most importantly the ability of the metric to predict the change in magnetization of the device. It is shown that for aspect ratios greater than roughly 2.5 the metric trends the same as the change in magnetization predicted by finite element simulations. The region of disagreement between the metric and the fully resolved finite element simulation is explained by tying back to underlying assumptions made during the formulation of the magnetometric demagnetization factor used in the analysis. The case is made for the figure of merit to be included in the analysis of strain-mediated antennas for its ability to find optimum designs while reducing the overall simulation run-time by an order of magnitude. / Master of Science / Many communication devices are readily available however there are a few key gaps in communication technology that are yet to be filled. Notably, communication in lossy environments using small scale, low frequency, devices has proven difficult due to the fundamental limits of antennas (a cell phone cannot communicate into a mine shaft for search and rescue operations, nor can they communicate underwater to submarines or divers for instance). A promising new approach of communication using smart magnetic materials is under consideration in this thesis. Specifically, the goal herein is to develop an analysis tool capable of predicting device performance without having to run computationally expensive/time consuming finite element simulations. In this thesis it is shown that the analysis tool is capable of predicting device performance while reducing the necessary simulation run-time by an order of magnitude. Using this tool, researches will be able to design better prototypes; moving one step closer to portable communication in lossy environments.