Academic literature on the topic 'Multiferroic Materials'

Magnetoelectric multiferroics are solid-state materials which exhibit a coupling between ferroelectric and magnetic orders. This phenomenon is known as the magnetoelectric (ME) effect. Multiferroic materials possess a wide range of potential applications in such fields as metrology, electronics, energy harvesting & conversion, and medicine. Multiferroic research is facing two main challenges. Firstly, scientists are continuously trying to obtain a material with sufficiently strong, room-temperature ME coupling that would enable its commercial application. Secondly, the measurement techniques used in multiferroic research are often problematic to implement in a laboratory setting and fail to yield reproducible results. The aim of the present work is to discuss three most commonly used methods in multiferroic studies; the lock-in technique, the Sawyer-Tower (S-T) circuit and dielectric constant measurements. The paper opens with a general description of multiferroics which is followed by mathematical representation of the ME effect. The main body deals with the description of the aforementioned measurement techniques. The article closes with a conclusion and outlook for future research.

As an entirely new perspective of multifunctional materials, multiferroics have attracted a great deal of attention. With the rapidly developing micro- and nano-electro-mechanical system (MEMS&NEMS), the new kinds of micro- and nanodevices and functionalities aroused extensive research activity in the area of multiferroics. As an ideal building block to assemble the nanostructure, cluster exhibits particular physical properties related to the cluster size at nanoscale, which is efficient in controlling the multiferroic properties for nanomaterials. This review focuses on our recent advances in multiferroic nanomaterials assembled with clusters. In particular, the single phase multiferroic films and compound heterostructured multiferroic films assembled with clusters were introduced detailedly. This technique presents a new and efficient method to produce the nanostructured multiferroic materials for their potential application in NEMS devices.

The community of material scientists is strongly committed to the research area of multiferroic materials, both for the understanding of the complex mechanisms supporting the multiferroism and for the fabrication of new compounds, potentially suitable for technological applications. The use of high pressure is a powerful tool in synthesizing new multiferroic, in particular magneto-electric phases, where the pressure stabilization of otherwise unstable perovskite-based structural distortions may lead to promising novel metastable compounds. Thein situinvestigation of the high-pressure behavior of multiferroic materials has provided insight into the complex interplay between magnetic and electronic properties and the coupling to structural instabilities.

Abstract Materials can be ferroelectric, having a spontaneous electric polarization that can be reversed by an external electric field, or they can be ferromagnetic, exhibiting spontaneous magnetization that is switchable by an applied magnetic field. However, until the 1960s, scientists did not expect that these two ferroic properties could co-exist in a single material. Today, materials exhibiting more than one of the primary ferroic properties are called multiferroics. Here, the primary ferroic properties can be ferroelectricity, ferromagnetism, antiferromagnetism, ferroelasticity, ferrotoroidicity or others. Basically, the multiferroic effect originates from the simultaneous breaking of space inversion and time-reversal symmetries. Multiferroics can be imagined as a pas de deux of electricity and magnetism. Recently, National Science Review interviewed Professor Sang-Wook Cheong from Rutgers University, who is one of the pioneering scientists in this field. Cheong talked about the multiferroics field, which has been fast developing since the early 2000s. His introductions and opinions on diverse multiferroic materials and potential multiferroic devices, as well as future research directions, may provide a useful resource for researchers both inside and outside the multiferroic research field.

Magnetoelectric multiferroics have attracted enormous attention in the past years because of their high potential for applications in electronic devices, which arises from the intrinsic coupling between magnetic and ferroelectric ordering parameters. The initial finding in TbMnO3 has triggered the search for other multiferroics with higher ordering temperatures and strong magnetoelectric coupling for applications. To date, spin-driven multiferroicity is found mainly in oxides, as well as in a few halogenides. We report multiferroic properties for synthetic melanothallite Cu2OCl2, which is the first discovery of multiferroicity in a transition metal oxyhalide. Measurements of pyrocurrent and the dielectric constant in Cu2OCl2 reveal ferroelectricity below the Néel temperature of ~70 K. Thus, melanothallite belongs to a new class of multiferroic materials with an exceptionally high critical temperature. Powder neutron diffraction measurements reveal an incommensurate magnetic structure below TN, and all magnetic reflections can be indexed with a propagation vector [0.827(7), 0, 0], thus discarding the claimed pyrochlore-like “all-in–all-out” spin structure for Cu2OCl2, and indicating that this transition metal oxyhalide is, indeed, a spin-induced multiferroic material.

The attempts to combine both the magnetic and ferroelectric properties in one material started in 1960s predominantly by the group of Smolenskii and Schmid [1. Dzyaloshinskii first presented the theory for multiferroicity in Cr2O3, which was soon experimentally confirmed by Astrov [5,. Further work on multiferroics was done by the group of Smolenskii in St. Petersburg (then Leningrad) [7, but the term multiferroic was first used by H. Schmid in 1994 [. These efforts have resulted in many fundamental observations and opened up an entirely new field of study. Schmid [ defined the multiferroics as single phase materials which simultaneously possess two or more primary ferroic properties. The term multiferroic has been expanded to include materials which exhibit any type of long range magnetic ordering, spontaneous electric polarization, and/or ferroelasticity. In the past decade, several hundreds of papers related to multiferroic materials and magnetoelectric effect have been published every year, making this topic one of the hottest areas in condensed matter physics from fundamental science as well as applications viewpoints. This article sheds light on recent progress about the developments of new multiferroics by combining unconventional magnetism and ferroelectricity with an emphasis on Bi based multiferroic materials. Specifically results of Ti doped BiMn2O5and Bi doped Co2MnO4multiferroics are discussed.

So far tens of multiferroic materials, with various chemical compositions and crystal structures, have been discovered in the past years. Among these multiferroics, some perovskite manganites with ferroelectricity driven by magnetic orders are of particular interest. In these multiferroic perovskite manganites, the multiferroic phenomena are not only quite prominent, but the involved physical mechanisms are also very plenty and representative. In this brief review, we will introduce some recent theoretical and experimental progress on multiferroic manganites, including the fascinating microscopic physics and very recently addressed experimental findings with attractive multiferroicity.

In the last decade, considerable attention has been focused on the search of new multiferroic materials and the ways of improvement of their magnetoelectric properties. In this short review, we survey the progress in study of multiferroics focusing the high temperature multiferroic bismuth ferrite and rare earth iron garnets. We discuss the recent results of investigation of domain walls in multiferroics, concentrating the most important magnetoelectric manifestations (electric polarization and magnetization), and the pinning effect appearing as clamping of ferroelectric and magnetic domain walls.

Multiferroism implies simultaneous presence of more than one ferroic characteristics such as coexistence of ferroelectric and magnetic ordering. This phenomenon has led to the development of various kinds of materials and conceptions of many novel applications such as development of a memory device utilizing the multifunctionality of the multiferroic materials leading to a multistate memory device with electrical writing and nondestructive magnetic reading operations. Though, interdependence of electrical- and magnetic-order parameters makes it difficult to accomplish the above and thus rendering the device to only two switchable states, recent research has shown that such problems can be circumvented by novel device designs such as formation of tunnel junction or by use of exchange bias. In this paper, we review the operational aspects of multiferroic memories as well as the materials used for these applications along with the designs that hold promise for the future memory devices.

Single-phase multiferroics that allow the coexistence of ferroelectric and magnetic ordering above room temperature are highly desirable, and offer a fundamental platform for novel functionality. In this work, a double perovskite multiferroic Pr2FeAlO6 ceramic is prepared using a sol-gel process followed by a quenching treatment. The well-crystallized and purified Pr2FeAlO6 in trigonal structure with space group R3c is confirmed. A combination of the ferroelectric (2Pr = 0.84 μC/cm2, Ec = 7.78 kV/cm at an applied electric field of 20 kV/cm) and magnetic (2Mr = 433 memu/g, Hc = 3.3 kOe at an applied magnetic field of 1.0 T) hysteresis loops reveals the room-temperature multiferroic properties. Further, the magnetoelectric effect is observed from the measurements of magnetically induced dielectric response and polarization. The present results suggest a new complex oxide candidate for room-temperature multiferroic applications.

Doutoramento em Física
The present PhD work aims the research and development of materials that exhibit multiferroic properties, in particular having a significant interaction between ferromagnetism and ferroelectricity; either directly within an intrinsic single phase or by combining extrinsic materials, achieving the coupling of properties through mechanic phenomena of the respective magnetostriction and piezoelectricity. These hybrid properties will allow the cross modification of magnetic and electric polarization states by the application of cross external magnetic and/or electric fields, giving way to a vast area for scientific investigation and potential technological applications in a new generation of electronic devices, such as computer memories, signal processing, transducers, sensors, etc. Initial experimental work consisted in chemical synthesis of nano powders oxides by urea pyrolysis method: A series of ceramic bulk composites with potential multiferroic properties comprised: of LuMnO3 with La0.7Sr0.3MnO3 and BaTiO3 with La0.7Ba0.3MnO3; and a series based on the intrinsic multiferroic LuMn1-zO3 phase modified with of Manganese vacancies. The acquisition of a new magnetron RF sputtering deposition system, in the Physics Department of Aveiro University, contributed to the proposal of an analogous experimental study in multiferroic thin films and multilayer samples. Besides the operational debut of this equipment several technical upgrades were completed like: the design and construction of the heater electrical contacts; specific shutters and supports for the magnetrons and for the substrate holder and; the addition of mass flow controllers, which allowed the introduction of N2 or O2 active atmosphere in the chamber; and the addition of a second RF generator, enabling co-deposition of different targets. Base study of the deposition conditions and resulting thin films characteristics in different substrates was made from an extensive list of targets. Particular attention was given to thin film deposition of magnetic phases La1-xSrxMnO3, La1-xBaxMnO3 and Ni2+x-yMn1-xGa1+y alloy, from the respective targets: La0.7Sr0.3MnO3, La0.7Ba0.3MnO3; and NiGa with NiMn. Main structural characterization of samples was performed by conventional and high resolution X-Ray Diffraction (XRD); chemical composition was determined by Electron Dispersion Spectroscopy (EDS); magnetization measurements recur to a Vibrating Sample Magnetometer (VSM) prototype; and surface probing (SPM) using Magnetic-Force (MFM) and Piezo-Response (PFM) Microscopy. Results clearly show that the composite bulk samples (LuM+LSM and BTO+LBM) feat the intended quality objectives in terms of phase composition and purity, having spurious contents below 0.5 %. SEM images confirm compact grain packaging and size distribution around the 50 nm scale. Electric conductivity, magnetization intensity and magneto impedance spreading response are coherent with the relative amount of magnetic phase in the sample. The existence of coupling between the functional phases is confirmed by the Magnetoelectric effect measurements of the sample “78%LuM+22%LSM” reaching 300% of electric response for 1 T at 100 kHz; while in the “78%BTO+22%LBM” sample the structural transitions of the magnetic phase at ~350 K result in a inversion of ME coefficient the behavior. A functional Magneto-Resistance measurement system was assembled from the concept stage until the, development and operational status; it enabled to test samples from 77 to 350 K, under an applied magnetic field up to 1 Tesla with 360º horizontal rotation; this system was also designed to measure Hall effect and has the potential to be further upgraded. Under collaboration protocols established with national and international institutions, complementary courses and sample characterization studies were performed using Magneto-Resistance (MR), Magneto-Impedance (MZ) and Magneto-Electric (ME) measurements; Raman and X-ray Photoelectron Spectroscopy (XPS); SQUID and VSM magnetization; Scanning Electron Microscopy (SEM) and Rutherford Back Scattering (RBS); Scan Probe Microscopy (SPM) with Band Excitation Probe Spectroscopy (BEPS); Neutron Powder Diffraction (NPD) and Perturbed Angular Correlations (PAC). Additional collaboration in research projects outside the scope of multiferroic materials provided further experience in sample preparation and characterization techniques, namely VSM and XPS measurements were performed in cubane molecular complex compounds and enable to identify the oxidation state of the integrating cluster of Ru ions; also, XRD and EDS/SEM analysis of the acquired targets and substrates implied the devolution of some items not in conformity with the specifications. Direct cooperation with parallel research projects regarding multiferroic materials, enable the assess to supplementary samples, namely a preliminary series of nanopowder Y1-x-yCaxØyMn1O3 and of Eu0.8Y0.2MnO3, a series of micropowder composites of LuMnO3 with La0.625Sr0.375MnO3 and of BaTiO3 with hexagonal ferrites; mono and polycrystalline samples of Pr1-xCaxMnO3, La1-xSrxMnO3 and La1-xCaxMnO3.
O trabalho de doutoramento presente tem por objectivo a pesquisa e desenvolvimento de materiais que manifestem propriedades multiferróicas, em particular com uma significativa interacção entre os fenómenos de ferromagnetismo e ferroelectricidade; seja de forma intrínseca em determinados materiais singulares, ou extrínseca ao combinar materiais que apresentam respectivamente fenómenos magnetoestritivo e de piezoelectricidade e em que geralmente o acoplamento se processa mecanicamente entre as fases. Esta hibridação de propriedades permite a modificação dos estados de polarização magnética ou eléctrica por aplicação dos campos externos complementares (eléctricos e/ou magnéticos), dando origem a uma vasta área de investigação científica e potenciais aplicações tecnológicas numa nova geração de dispositivos electrónicos como memórias, processadores, transdutores, sensores, etc. O trabalho experimental inicial consistiu na síntese química de óxidos sob a forma de pós nanométricos, pelo método de pirólise da ureia; As séries de compósitos maciços com potenciais propriedades multiferróicas compreendem: LuMnO3 com La0.7Sr0.3MnO3 e BaTiO3 com La0.7Ba0.3MnO3; e uma série baseada na modificação com lacunas de Manganésio da fase multiferróica intrínseca LuMn1-zO3. A aquisição de um novo sistema de deposição por RF sputtering, no Departamento de Física da Universidade de Aveiro, contribuiu para a proposta de estudo análogo de amostras multiferróicas sob a forma de filmes finos e multicamadas. Além da estreia operacional do equipamento foram efectuadas algumas melhorias técnicas e funcionais de que se destacam: o desenho e construção das ligações eléctricas do aquecedor; de portadas, protecções e respectivos suportes para os magnetrões e para o “porta substratos”; a adição de dois controladores de fluxo de gás permitindo a introdução controlada de Árgon e de atmosfera activa de O2 ou N2 durante a deposição; e a adição de uma segunda fonte e controlador RF permitindo a co-deposição simultânea de filmes a partir de dois alvos diferentes. O estudo base sobre as condições de deposição e das características dos filmes finos resultantes em diferentes substratos foi efectuada a partir de uma extensa lista de alvos. Atenção particular foi dada à deposição de filmes finos das fases magnéticas de La1-xSrxMnO3, La1-xBaxMnO3 e da liga Ni2+x-yMn1-xGa1+y a partir dos correspondentes alvos La0.7Sr0.3MnO3; La0.7Ba0.3MnO3 e NiGa com NiMn. A caracterização estrutural das amostras foi efectuada com Difractometria por Raios-X (XRD) convencional e de elevada resolução; determinação da composição química foi essencialmente realizada por Espectroscopia de Dispersão de Electrões (EDS); medidas de magnetização foram executadas com recurso a um protótipo de Magnetometro por Vibração da Amostra (VSM) e as medidas de análise de superfície utilizaram Microscopia de Ponta (SPM) nas vertentes de piezo resposta (PFM) e de força magnética (MFM). Os resultados obtidos nos compósitos maciços (LuM+LSM e BTO+LBM) demonstram claramente que as amostras satisfazem os objectivos propostos em termos de composição pureza das fases, com eventual conteúdo em óxidos espúrios inferior a 0.5%. Imagens obtidas por SEM confirmam a compactação dos grãos e distribuição de tamanhos em torno dos 50 nm. Condutividade eléctrica, intensidade da magnetização e a dispersão da resposta em Magneto-Impedância são coerentes com a proporção relativa da fase magnética em cada amostra. A existência de um acoplamento entre as fases funcionais é evidenciada por medidas de efeito Magneto-Eléctrico na amostra “78%LuM+22%LSM” que apresenta uma resposta eléctrica de ~300% para 1 Tesla a 100 kHz; enquanto que na amostra “78%BTO+22%LBM” se assinala a transição estrutural da fase magnética a ~350 K resulta na inversão do comportamento do coeficiente ME. Um sistema de Medidas de Magneto-Resistência foi totalmente desenvolvido e montado desde a fase conceptual até ao estado operacional; permite testar amostras de 77 a 350 K em função do campo magnético até 1 Tesla, e rotação horizontal de 360º; o sistema foi também desenhado para poder efectuar medidas de efeito de Hall e permitir upgrades. Ao abrigo de protocolos de colaboração estabelecidos com diversas instituições nacionais e internacionais, foram realizados cursos de formação complementar e caracterização de amostras em técnicas como Magneto Resistência (MR), Magneto Impedância (MZ) e efeito Magneto Eléctrico (ME); Espectroscopia Raman e Fotoelectrónica de Raios-X (XPS); Magnetização via sistemas SQUID e VSM; Microscopia de Ponta em Piezo resposta (PFM) e Espectroscopia de excitação em largura de banda (BEPS); Espectroscopia de Rutherford por Retro dispersão (RBS); Difracção de Neutrões em pós (NPD) e Correlações de Perturbação Angular (PAC) Colaboração em projectos de investigação fora do âmbito dos materiais multiferróicos permitiu ampliar e versatilizar experiencia em técnicas de preparação e caracterização de amostras, nomeadamente medidas de VSM e XPS permitiram identificar os estados de oxidação dos clusters de iões de Ruténio que integram complexos moleculares utilizados em catalisadores; A certificação por XRD e SEM/EDS do conjunto dos alvos e amostragem dos substratos adquiridos implicou a devolução de alguns itens com por falta de conformidade com as especificações. Cooperação directa em projectos de investigação paralelos sobre materiais multiferróicos permitiu o acesso a amostras suplementares, nomeadamente a uma série nano pós de Y1-x-yCaxØyMn1O3 e de Eu0.8Y0.2MnO3; a series de compósitos microestruturados de LuMnO3 com La0.625Sr0.375MnO3 e de BaTiO3 com ferrites hexagonais; e a diversas amostras poli- e mono-cristalinas de Pr1-xCaxMnO3, La1-xSrxMnO3 e La1-xCaxMnO3.
FCT - SFRH/BD/25011/2005

Thesis (Ph. D.) -- University of Maryland, College Park, 2008.
Thesis research directed by: Dept. of Physics. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

Notre étude porte sur des matériaux à effets relativistes importants. L'hamiltonien semi-relativiste, couplé aux équations de Maxwell (EM), permet de déduire les sources de courant et de densité, incluant des termes de second ordre (polarisations de spin et de Darwin). Différents modèles sont développés par expansion des EM. L'étude ab initio montre que (1) le désordre atomique peut produire le ferrimagnétisme (FM) dans GaFeO3 (GFO) multiferroïque, (2) les états 3d Fe des octaèdres déformés ont une levée de dégénérescence tétraédrique (théorie du champ cristallin), (3) la polarisation électrique concorde avec l'expérience, (4) le mécanisme magnétoélectrique (ME) direct est insuffisant pour expliquer le ME observé. Pour Cr2O3, le calcul de l'état massif sous contraintes biaxiales n'explique pas son FM, la taille de l'échantillon ou l'excès d'oxygène pourrait de fait être important. Enfin, nous avons développé le XAS et le XMCD dans le code VASP et calculé ces spectres pour GFO
We studied the physics of materials where relativistic effects are important. We first coupled the semi-relativistic Hamiltonian with the Maxwell's equations, and derived the current and density sources, which included second-order terms like the spin and Darwin polarizations. Different models were developed, by expanding the Maxwell's equations. We then performed ab initio studies to explain (1) site disorders as the origin of ferrimagnetism in multiferroic GaFeO3 (GFO), (2) crystal-field theory where the Fe 3d states at the deformed octahedra have tetrahedral splittings, (3) the electric polarization as a function of temperature, and (4) the insufficiency of the direct magnetoelectric (ME) mechanism to explain observed ME behavior. For Cr2O3, bulk calculations for different biaxial strains failed to explain its ferromagnetism, indicating that size or excess-O effects might be important. Finally, we implemented XAS and XMCD in VASP and computed these spectra for GFO

Photoferroelectrics, which is defined as the interaction of ferroelectric materials with light, has attracted renewed attention recently and emerged as a topic of both fundamental interest and technological importance. It not only provides potential applications in sensors and photovoltaic devices but also offers a fertile playground to gain insight into the physics of ferroelectricity. As a prominent example, the bulk photovoltaic effect manifested in the ferroelectric materials under illumination gives rise to an anomalous open-circuit photovoltage exceeding the bandgap as well as a light polarisation-dependent photocurrent, offering an alternative approach to boost the solar energy conversion efficiency. Although it has been established for decades, the field is still in its fancy and many fundamental issues remain to be resolved to fully exploit its potential. In the first part of this thesis, we focus on the photoelectric processes in the bulk photovoltaic effect of bismuth ferrite to unravel respectively the essential role of the sub-bandgap levels, its correlation with ferroelectric polarization and role of domain walls in conduction of photovoltaic current. Results demonstrate the sub-bandgap levels is at the electronic origin of the bulk photovoltaic effect in bismuth ferrite. The activity of the sub-bandgap levels in the photoelectric processes can be effectively utilized to tailor the ferroelectric photovoltaic performance. Also, contrary to the common intuition, we prove the independence of the bulk photovoltaic effect on the ferroelectric polarization. We also found that the ferroelectric domain walls can facilitate the conduction and collection of the photocurrent originated in the bulk photovoltaic effect despite its adverse effect on the photovoltage. Inspired by the abundant phenomena in the photoferroelectric field, we explored the light-induced reversible manipulation of the ferroelectric polarization in a deterministic way. This interesting issue is successfully addressed in this thesis by utilizing a combination of the bulk photovoltaic effect and a nanoscale electrode. The collection of photocurrent by an atomic force microscope tip generates a giant electric field locally, enabling ferroelectric switching. By tuning the direction of the photocurrent via either illumination areas or light polarization, the ferroelectric polarization can be reversibly controlled. At the last part of the thesis, we creatively generalised the bulk photovoltaic effect, which was originally constrained to the non-centrosymmetric materials, to a universal effect allowed in all the semiconductors irrespective of their symmetry by the mediation of the flexoelectric effect. This new photovoltaic effect, termed as flexo-photovoltaic effect, may offer a new mechanism to enhance solar cell efficiency. The research works studied in this thesis not only provide fundamental insights into the interactions of ferroelectrics with light but also largely expand the scope of photoferroelectrics into centrosymmetric materials.

Multiferroic materials have recently begun to attract significant scientific interest due to their potential applications in the design of modern electronic devices. Currently, the magnetic properties of materials form the basis of our electronic data storage and have the potential to enhance the logic operations performed in electronic devices (such as computers and sensors). Non-volatile magnetic memory is used in data storage devices, such as the hard drives found in personal computers, where data is encoded via the magnetisation state of magnetic domains in the device with one of two states: either up or down (M ↑ or M ↓); the state is determined or changed by interacting with the magnetic flux about the domain. Furthermore, in current computing and sensor technology, logic operations are performed with arrays of transistors; however, in spintronics ("spin transport electronics") the electric current itself is spin polarised and there is data encoded in the current itself. Circuit elements in such a system are magnetic devices that interact with the electron spin.Magnetoelectric multiferroics are materials that have both a spontaneous ferroelectric polarisation (P) and magnetic magnetisation (M). Polarisation may be manipulated by an electric field and magnetisation by a magnetic field, hence the potential of multiferroics lies in the coupling between the two degrees of freedom and the manipulation of magnetisation by an applied electric field and vice versa. The properties of a magnetic device could be altered "on-the-fly" by applying an electric pulse, and in the context of the examples provided this would greatly diversify the logic elements in spintronic circuits. Furthermore, with both polarisation and magnetisation a multiferroic domain can take on one of four states (M ↑ P ↑, M ↑ P ↓, M ↓ P ↑, or M ↓ P ↓) dramatically increasing data storage density over the current binary system.Lutetium ferrite (LuFe2O4) is a multiferroic material in which both the magnetisation and polarisation arise from the iron sites and with strong iron-iron correlations the material is a promising candidate as a high temperature multiferroic. The material has a layered structure with bilayers of FeO separated by single layers of LuO on a hexagonal lattice. Frustrated 2D charge order exists below 550 K which transitions to 3D charge order below 330 K and simultaneously frustrated ferrimagnetic order exists in the multiferroic phase below 250 K. X-ray and neutron scattering experiments have been performed in order to characterise the ferroelectric and ferrimagnetic order and magnetoelectric coupling in this material.Resonant x-ray scattering (RXS) was performed on the Material Science beamline of the Swiss Light Source where the energy dependence of the superlattice reflections corresponding to the charge order was collected. Non-linear regression using a custom Levenberg-Marquadt algorithm was applied in order to extract the anomalous scattering factors which demonstrated the superlattice reflections were described by a charge order model. Furthermore, the chemical shift was shown to correspond to full Fe2+/Fe3+ charge disproportionation. The absence of any polarisation or azimuthal dependence, shown by resonant x-ray scattering data collected on the ID20 beamline of the European Synchrotron Radiation Facility, confirmed the prediction of Nagano et al. that the orbital moments of the Fe2+-sites exist in a disordered glassy state.X-ray absorption near edge structure (XANES) calculations were performed using the FDMNES program in order to assess the validity of the anomalous scattering factors obtained in the RXS experiment and to further test the charge order model. It was shown that the characteristic features of the experimentally determined functions can be qualitatively reproduced by calculations using the known charge order model. Furthermore, these functions were shown to reproduce the phase of the RXS data further demonstrating that the reflections result from a pure charge ordered phase.Inelastic neutron scattering performed on the PUMA triple axis spectrometer of the FRMII demonstrated that magnetic critical scattering is observed at 250 K. A broad peak in the temperature dependence is observed rather than the characteristic divergence of a magnetic transition: this is attributed to broadening of the transition by the distribution of oxygen stoichiometry in the sample and ferroelectric fluctuations integrated into the data due to poor c-axis resolution. Pyroelectric current and magnetometry measurements demonstrate a peak in the magnetic susceptibility and a step in the polarisation at approximately 215 K, well below the magnetic transition. Elastic neutron scattering experiments performed on the E2 flat cone diffractometer of the Helmholtz-Zentrum Berlin demonstrate these features correspond to a 2D-to-3D magnetic transition that has previously only been predicted by anomalies in other measurements.An applied field study performed by neutron scattering on the E2 flat cone diffractometer of the Helmholtz-Zentrum Berlin and x-ray scattering on the PX1 protein crystallography beamline of the Australian synchrotron demonstrate the control of the magnetic domain population with an electric field, contrary to other recent reports on this topic. Furthermore, the observed magnetoelectric coupling is inconsistent with current models of the magnetic structure of this system. The x-ray measurements demonstrate a disorder-to-order effect by the applied electric field as 3D order is preferred with an increase in the intensity of all satellites.Temperature dependent x-ray powder diffraction data collected on the Powder Diffraction (PD) beamline of the Australian Synchrotron has demonstrated anisotropic thermal expansion with negative thermal expansion of the c-axis in this material. Electron density mapping by Fourier analysis shows the disorder of the oxygen between the electrically static Lu ions and the neighbouring Fe ions, as electron hopping between Fe2+ and Fe3+ leading to a corresponding variation on the Fe-O bond length. Reversible structural distortions are observed indicating a piezoelectric effect in this material caused by the crushing during sample preparation. Furthermore, weak reflections in the x-ray patterns, corresponding to a monoclinic sublattice, suggest a monoclinic distortion of the oxygen sites which is supported by neutron powder diffraction collected on the ECHIDNA instrument of the OPAL reactor.

Multiferroic materials, in which two or more ferroic ordering take place in the same phase, have driven major interest in the last few years, not only due to the possibility of exploring novel physical properties in those materials, but also the implications that such properties show in novel technological applications. From those materials, the especially interesting are those in which the ferromagnetic (FM) and ferroelectric (FE) ordering take place, due to their direct application in magnetodielectric devices. In the field of multiferroic materials such materials could play an important role in a new generation of none volatile magnetic random access memories (M RAM), in which a sufficiently strong magnetodielectric coupling could allow for the modification of the magnetic state, not only with a magnetic field, but with an electric field. This fact would allow for a dramatic reduction in energy consumption and would promote the further technological integration (the major commercial drawback of MRAMs), due to the fact that an electric field, contrary to the magnetic field, can be applied locally. Additionally, such multiferroic materials could prove useful in magnetic tunnel junctions, in which the ferroelectric and ferromagnetic nature would allow them to codify four resistive states, instead of the traditional two states of ferroelectric or ferromagnetic junctions, allowing for the implementation of a generation of four state memories. The materials with perovskite structure, ABB"03 (A=Rare Earth, Bismuth, Lead and Yttrium), bring a broad spectrum of possibilities when it comes to design of multifunctional materials. This is due to the wide variety of A, B, B" cations that are compatible with such structure. However, in the case of R(NiMn)03, such oxides have been poorly studied and many detailed studies, both in bulk and thin films are needed. The cation selection of B and B' seems to transform the paramagnetic ordering (PM) into FM below room temperature. The multiferroicity of these materials is typically provided by the A cation of the perovskite formula, which can be Bi or Pd, in order to create a Type 1 multiferroic. In this type of materials, i.e: Bi2NiM n06, the ferroelectricity and ferromagnetism arose by separate mechanisms, the FE is provided by the A cation, with so called long pair electrons, which are free electrons in the valence band that do not participate in any chemical reaction in the compound, while the Ni2+(d8) and (M n4+) (d3) provides the FM. However, even though the materials are multiferroic, their magnetodielectric coupling, crucial for future industrial applications, is weak, due to the different mechanisms that provide their FM and FE ordering. On the other hand, the FE induction by geometrical distortion of the perovskite lattice, for example in YM n03, is an interesting case since rotations of the M nO6 octahedrons promote an important structural change, in which the oxygen atoms move closer to the Y and, due to a large dipole interaction, generate a stable FE state. Moreover, the deformation of the unit cell generates a weak spin canting on the Mn cations, that can be promoted by Li doping or lattice distortions. This behavior could prove useful in the R(NiM n)06 family, which shows strong FM . This thesis is devoted to the study of R(Ni0.5M n0.5)03 (Y,Sm, Nd and Pr) and Bi(Fe0.5M n0.5)06 grown in thin films by pulsed laser deposition technique. Firstly, this thesis focuses on the growth and characterization of thin films of Y(Ni0.5M n0.5)03 (YNM 0) on strontium titanate substrates SrTiO3(001) (STO). The influence of the deposition parameters, such as temperature, fluence and ablation frequency, on the morphology and crystalline quality of the films is investigated. The study reveals that the YNMO films grown on STO(001,011 and 111) substrates are epitaxial and that their crystalline quality and epitaxial relationship are similar to those of the YMO compound. In particular, it is observed that a single out of plane domain is the norm for all the substrate orientations, while there are various in-plane domains. Moreover, chemical composition studies reveal Ti diffusion from the substrate to the YNMO film when STO(111) substrates are used. Once the growth conditions of YNMO are optimized, the magnetic and dielectric properties are studied. All the films show a paramagnetic to ferromagnetic transition at a temperature around 95K, with a magnetic moment of YNMO(001) = 4.35µB/f.u, YNMO(100) = 4,4 µB/f.u and YNMO(101) = 3,7µB/f.u, confirming the ferromagnetic nature of the samples. The dielectric characterization reveal a FE ordering on the YNMO films, and what is more, the existence of a dielectric anisotropy on the films, that is characterized by the absence of ferroelectric response on YNMO samples deposited on STO(001), while YNMO samples on STO(111) show a strong FE response. This anisotropy could be explained, according to recent theoretical studies, in the improper origin of the observed ferroelectriciy. The coexistence of FM and FE response shows in a conclusive manner the multiferroic nature of the YNMO compound. Secondly, studies similar to those previously presented are performed for thin films of R(Ni0.5Mn0.5)O3 (Sm, Nd and Pr) compounds grown on STO(001). In this case the deposition temperature turns out to play a crucial role on the epitaxial growth of all the studied compounds. It is shown that the ratio between the b/a lattice parameters influences the epitaxial growth of the films, being the decisive factor between single or multi domain films. All the samples show a PM to FM transition at temperatures around 190K Finally, films of Bi(Fe0.5Mn0.5)O6 have been grown on STO(001) substrates. The films are epitaxial and grow under epitaxial strain. Samples show a FM behavior at room temperature with a weak signal of 7,42 emu/cm3 and 0,4 µB/f.u(Fe-Mn). The dielectrical characterization shows the influence of external magnetic fields on the dielectric properties of the film above room temperature.
Los materiales multiferroicos, en los que dos o más ordenes ferroicos tienen lugar en la misma fase, ha despertado gran interés en los últimos años debido, no solo al hecho de explorar nuevas propiedades físicas en los materiales, sino también a las implicaciones de las nuevas propiedades funcionales en las aplicaciones tecnológicas. De dichos materiales resultan especialmente interesantes aquellos que presentan un orden ferroeléctrico (FE) y ferromagnético (FM) debido a su aplicación directa en dispositivos magnetoelectrónicos. En este ámbito los materiales multiferroicos podrían tener una gran relevancia en una nueva generación de memorias magnéticas RAM (MRAM) de control eléctrico, no volátiles, en las que, si el acoplamiento magnetoeléctrico es suficientemente grande, se podría modificar el estado magnético no con un campo magnético sino con un campo eléctrico. Este hecho permitiría una reducción radical en el consumo de potencia y favorecería a su vez una mayor integración (la principal desventaja de las MRAMs para competir en el mercado), ya que el campo eléctrico, a diferencia del campo magnético, puede aplicarse de forma muy localizada. Por otro lado, dichos materiales multiferroicos podrían emplearse en una nueva generación de uniones túnel, en las que el carácter ferroeléctrico y ferromagnético permitiría codificar información en cuatro estados resistivos en lugar de en dos, como viene siendo hasta ahora en las convencionales uniones túnel magnéticas o ferroeléctricas, dando lugar a una nueva generación de memorias de cuatro estados. Los materiales con estructura perovskita, ABB '03, (A=Tierra Rara, Bismuto, Plomo e Ytrio) ofrecen una gran versatilidad a la hora de diseñar materiales funcionales debido a la gran variedad de cationes A, B y B' compatibles con tal estructura. Sin embargo en el caso de R(NiMn)03, estos óxidos han sido poco estudiados y muchos carecen de estudios detallados tanto en forma másica como en capa fina. Esta selección de cationes en la posición B y B' parece transformar la estructura perovskita la cual típicamente presenta un ordenamiento paramagnético (PM) en FM a temperaturas inferiores a la ambiente. El carácter multiferroico de estos materiales es típicamente aportado por el catión A en la formula perovskita, el cual puede ser un átomo de Bi, o Pb, para crear un multiferroico tipo 1. En los materiales de este tipo, por ejemplo el Bi2NiMnO6, la ferroelectricidad y el ferromagnetismo provienen de fuentes diferentes, el carácter FE es aportado por el catión A con -lone pairs electrons-, los cuales son electrones libres en la banda de valencia que no participan en las reacciones químicas del compuesto, mientras la combinación Ni2+ (d8) and Mn4+ (d3) aporta el FM. Pese al carácter multiferroico de estos materiales su acoplamiento magnetoelectrico, indispensable para sus aplicaciones industriales futuras, es débil, puesto que su FE y FM provienen de efectos independientes. Por otra parte la inducción de FE por distorsiones geométricas de la celda perovskitas, como es el caso de YMnO3 (YMO), es un caso interesante de considerar ya que la rotación de los octaedros Mn05 genera un cambio estructural importante, en el cual los oxígenos se desplazan a una posición más cercana al Y, esto sumado a una larga interacción de los dipolos conduce al material a un estado FE estable. Además la deformación de la celda genera un débil FM en este material, el cual proviene un pequeño giro en los espines del Mn ya sea debido a un dopaje con Li o por la deformación de la celda. Este comportamiento podría resultar interesante en la familia de perovskitas R(NiMn)03 las cuales presentan un fuerte FM. Esta tesis está dedicada al estudio de la perovskitas R(Ni0.5Mn0.5)O3 (Y, Sm, Nd y Pr) y Bi(Fe0.5Mn0.5)O6 crecidas en capa fina usando la técnica de depósito mediante ablación por láser pulsado. En primer lugar, esta tesis se centra en el crecimiento y caracterización de capas finas del compuesto Y(Ni0.5Mn0.5)O3 (YNMO) sobre substratos de titanato de estroncio, SrTiO3(001) (STO). Se estudia la influencia de los parámetros de depósito tales como temperatura, fluencia y frecuencia de ablación sobre la morfología y la calidad cristalina de las capas obtenidas. El estudio pone de manifiesto que las capas de YNMO crecidas sobre substratos de STO(001,011 y 111) son epitaxiales de YNMO y que la calidad cristalina y las relaciones epitaxiales entre la capa y el substrato son semejantes a las obtenidas en el compuesto YMO. En particular se observa un único dominio cristalino fuera del plano independientemente de la orientación del sustrato, mientras que dentro del plano se presentan varios dominios cristalinos. Por otra parte, los estudios de composición química revelan una difusión de Ti desde el sustrato hacía la capa de YMNO cuando se utilizan substratos STO(111).. Una vez optimizadas las condiciones de crecimiento del compuesto YNMO, se estudian sus propiedades magnéticas y dieléctricas. Todas las capas presentan una transición de fase paramagnetica a ferromagnética a una temperatura alrededor de 95K con un momento magnético de YNMO(001)= 4.35µB/f.u, YNMO(100) = 4,4 µB/f.u and YNMO(101) = 3,7µB/f.u, confirmando el carácter ferromagnético de las muestras. La caracterización dieléctrica revela el carácter FE de las capas de YNMO y lo que es más interesante, la existencia de anisotropía dieléctrica en las capas, ésta se pone de manifiesto en la ausencia de respuesta FE en capas YNMO sobre STO(001) que contrasta con la fuerte respuesta de las capas de YNMO sobre STO(111). Esta anisotropía puede tener su origen, a la luz de los recientes estudios teóricos, en el carácter impropio de la ferroelectricidad observada, a la luz de recientes estudios teóricos. La coexistencia de FM y FE muestra de manera conclusiva el carácter multiferroico del compuesto YNMO. En segundo lugar se han realizado estudios similares a los anteriores para el caso de capas finas de los compuestos del tipo R(Ni0.5Mn0.5)O3 (Sm, Nd y Pr) crecidas en STO(001). En este caso la influencia de la temperatura de depósito resulta ser un factor importante para la obtención, en todos los compuestos estudiados, de crecimiento epitaxial. Se observa que el cociente b/a entre las constantes red juega un factor importante en la epitaxia de las capas, siendo este cociente un factor determinante en el crecimiento mono-dominio o multi-dominio de las capas. Todas las muestras presentan transiciones PM a FM a temperaturas alrededor de 190K. Por último, se han crecido y estudiado capas finas del compuesto Bi(Fe0.5Mn0.5)O6 depositadas sobre STO(001). Las capas obtenidas son epitaxiales y crecen sometidas a estrés inducido por el substrato. Presentan comportamiento FM a temperatura ambiente pero con una débil señal de 7,42 emu/cm3 y 0,4 µB/f.u(Fe-Mn). La caracterización dieléctrica pone de manifiesto la influencia, a temperaturas superiores a la ambiente, de la presencia de campo magnético sobre las propiedades dieléctricas.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2015.
This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references.
Complex oxide thin films offer unique functionalities which can potentially extend the utility of current storage, processing and optical isolator technologies. In this thesis, we present three categories of studies on complex oxide growth using pulsed laser deposition (PLD) and structural, magnetic, magneto-optical and ferroelectric characterization. We first focused on enhancing integrated magneto-optical isolator performance by improving the growth method of magneto-optical Ce1Y2Fe5O12 (Ce:YIG) films. The spectral and substrate orientation dependence of the magneto-optical figure of merit of epitaxial Ce: YIG on GGG substrates show very high magneto-optical figure of merit (379-400° dB-1 at [lambda] = 1550 nm for all substrate orientations). The thermal budgets of Ce: YIG growth on ShN4 (2 high temperature PLD steps and a rapid thermal anneal, RTA), silicon-on-insulator substrates (a high and a low temperature PLD step and a RTA) and optical resonator chips (one PLD step, one RTA, YIG seed layer from the top) were progressively reduced to achieve improved integrated optical isolators with low insertion loss of 7.4 ± 1.8 dB and an isolation ratio of 13.0 ± 2.2 dB. We demonstrated that the ferrimagnetic insulator YIG thin films (Y3Fe5O12) epitaxially grown on GGG substrates achieve ultralow Gilbert damping of spin waves ([alpha] = 2.2-7 x 10-4 ), which enable em-long in-plane propagation of spin waves. This demonstration enables researchers to fabricate near-dissipationless magnon-based logic computers. Finally, we present a substitutionally-doped perovksite, STCo30 (Sr Ti0.70 CO0.30 O3-[delta]) integrated on Si, STO (100), and on Nb:STO substrates. This perovskite oxide has been found to exhibit ferroelectricity and magnetism at room temperature. Experimental results on magnetism, ferroelectricity and structure were reproduced using density functional theory simulations.
by Mehmet Cengiz Onbaş̧lı.
Ph. D.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2014.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 133-150).
To respond to the growing demand for smart and connected devices, such as smartphones, tablet PCs arid other mobile hardware, while meeting the needs for increased power efficiency, miniaturization and reduced manufacturing costs, new material solutions need to be considered. These should address the shortcomings of incumbent semiconductor-based technologies which provide a limited number of functionalities, suffer from high power consumption and heat dissipation, and whose conventional planar processing is increasingly complex and resource-intensive. Potential replacement materials include complex oxides, which exhibit interesting physical phenomena such as superconductivity, colossal magnetoresistance and multiferroicity. New functionalities are especially found at interfaces between two oxides, including emergent electronic states like two-dimensional electron gases, enhanced ionic transport and magnetoelectric coupling, among many other. In this this thesis, we focus on self-assembled oxide nanocomposites, which elegantly organize into vertical nanostructures via spontaneous phase-separation, naturally forming numerous such heterointerfaces. These provide a rich playground for studying interfacial effects, which could be used in future devices, and the self-assembly promises cheap arid high throughput manufacturing providing it can be integrated into useful architectures. BiFeO₃-CoFe₂O₄ self-assembled nanocomposites, in particular, have been studied for the magnetoelectric coupling that takes place between the ferrimagnetic spinel phase, which forms discrete vertical pillars, arid the ferroelectric perovskite phase, which forms a matrix that surrounds the spinel pillars. Here, after an in-depth study of the mechanisms responsible for the formation of this self-assembled nanostructure, we develop a templating method enabling the precise control over the morphology of the film, resulting in useful structures for potential devices like magnetoelectric memories and logic devices. To study the structural, magnetic and electrical properties of our samples, a set of experimental and theoretical methods is developed, adapted to the unique requirements of these thin film nanostructures with iicron-scale ordering. Using finite element analysis and micromagnetic modeling, the effect of the strain-mediated magnetoelectic coupling on the magnetic switching of the CoFe₂O₄ nanopillars is predicted. Scanning Probe Microscopy is also used to characterize the local ferroelectric and magnetic behavior, and observe, for the first time in these templated composites, electrically-induced magnetic switching of the pillar magnetization. The tools and methods developed in this thesis could pave the way towards a wider use of templated self-assembly to leverage the promising properties of oxide heterointerfaces and enable their use in future devices with low manufacturing costs.
by Nicolas M. Airmon.
Ph. D.

Esta tesis trata sobre los magnetoel ectricos multiferroicos, una clase relativamente nueva de materiales descubiertos a mediados del siglo pasado, que presentan simultaneamente ferroelectricidad y magnetismo. El BiFeO3 (BFO) es un oxido con estructura perovskita, el cual es uno de los pocos materiales multiferroicos a temperatura ambiente. Sin embargo, como sus temperaturas de ordenamiento ferroel ectrico y anti-ferromagn etico son relativamente altas (alrededor de 1100 K y 640 K, respectivamente), las respuestas electromec anica y magnetoel ectrica del BFO son relativamente peque~nas en condiciones ambientales. En esta tesis se utilizamos m etodos ab-initio, basados en la teor a del funcional de la densidad (DFT), para estudiar las propiedades del BFO, y proponemos una posible estrategia para la mejora de su respuesta. Hemos utilizado m etodos de primeros principios para llevar a cabo una b usqueda sistem atica de las fases potencialmente estables de este compuesto. En la que consideramos las distorsiones m as comunes entre los oxidos de tipo perovskita y encontrando un gran n umero de m nimos locales de la energ a. En este trabajo se discute la gran variedad de estructuras de baja simetr a descubiertas, as como las implicaciones de estos hallazgos en cuanto a los trabajos experimentales mas recientes sobre este compuesto. Tambi en se llev o acabo un estudio de la soluci on s olida Bi1􀀀��xLax FeO3 (BLFO) formada por la BFO y la LaFeO3 (LFO)antiferromagnetica parael ectrica. Se discuten las transformaciones estructurales que sufre BLFO en funci on del contenido de La, y la conexi on de nuestros resultados con los estudios cristalogr a cos existentes. Hemos encontrado que, en una amplia gama de composiciones intermedias, la BLFO presenta fases que son esencialmente degeneradas en energ a. Adem as, los resultados sugieren que para este compuesto, dentro de esta regi on morfotr opica inusual, se puede utilizar un campo el ectrico para inducir transiciones parael ectrico a ferroel ectrico. Tambi en se discuten las propiedades de respuesta de la BLFO y se demuestra que se pueden mejorar signi cativamente en los materiales puros BFO y LFO, mediante la sustituci on parcial de los atomos Bi y La . Por otra parte, se presenta tambi en un estudio de primeros principios de la BFO a altas presiones. En el cual explicamos la naturaleza de las transiciones de fase del BFO, que simult aneamente involucran un colapso del volumen, un cambio en el estado de spin de High spin a Low spin y una metalizaci on producto del desorden magn etico en la nueva fase. Por ultimo presentamos los resultados preliminares de un proyecto en marcha, en el cual estamos modelando la energ etica de las rotaciones de los octaedros de oxigeno en los oxidos de estructura perovskita. Para ello se ha expandido la energ a en funci on de los par ametros de orden que caracterizan dichas rotaciones hasta cuarto orden. Hemos teado el modelo a los resultados de nuestros c alculos de primeros principios y realizado una comprobaci on cuidadosa de su valides, determinando que es necesario recurrir a ordenes mas altos en nuestra teor a.
This work is about magnetoeltric multiferroics, a relatively new class of ma- terials discovered by the mid of the past century, which involve simultaneously ferroelectricity and magnetism. Perovskite oxide BiFeO3 (BFO) is one of the few multiferroic materials at room temperature. However, as its ferroelectric and anti- ferromagnetic transition temperatures are relatively high (about 1100 K and 640 K, respectively), BFO's electromechanical and magnetoelectric responses are small at ambient conditions. In this thesis we used ab-initio methods, based on density functional theory, to study the basic properties of BFO and proposed possible strategies for enhancing its response. We used rst-principles methods to perform a systematic search for potentially stable phases of BFO. We considered the distortions that are most common among perovskite oxides and found a large number of local minima of the energy. We discussed the variety of low-symmetry structures discovered, as well as the implications of these ndings as regards current experimental work on this compound. We also carried out a study of the Bi1􀀀�xLaxFeO3 (BLFO) solid solution formed by multiferroic BFO and the paraelectric antiferromagnet LaFeO3 (LFO). We dis- cussed the structural transformations that BLFO undergoes as a function of La content and the connection of our results with the existing crystallographic stud- ies. We found that, in a wide range of intermediate compositions, BLFO presents competitive phases that are essentially degenerate in energy. Further, our results suggested that, within this unusual morphotropic region, an electric eld might be used to induce various types of paraelectric-to-ferroelectric transitions in the compound. We also discussed BLFO's response properties and showed that they can be signi cantly enhanced by partial substitution of Bi/La atoms in the pure BFO and LFO materials. We analyzed the atomistic mechanisms responsible for such improved properties and showed that the e ects can be captured by simple phenomenological models that treat explicitly the composition x in a Landau-like potential. Furthermore, we performed a rst-principles study of BFO at high pressures. Our work revealed the main structural change in Bi's coordination and suppression of the ferroelectric distortion, electronic spin crossover and metallization, and mag- netic loss of order e ects favored by compression and how they are connected. Our results are consistent with and explain the striking manifold transitions observed experimentally We conclude our thesis presenting the preliminary results of an ongoing project in which we are modeling the energetics of the oxygen octahedra rotations in per- ovskite oxides. The model is tted to the rst-principles results and a careful check of its validity is carried out.

The monograph is devoted to describing the methods of catastrophe theory and building on the basis of these methods, phenomenological models of phase transitions in solids. Methods of constructing structurally stable normal forms of functions, including functions that are imposed on the symmetry conditions. The classification of phenomenological models of phase transitions for two interacting one-component order parameter, two-component and three-component order parameters the number of control parameters varied in the experiment. Theoretical dependence of the anomalies of the physical properties of the models are compared with experimental data in ferroelectrics, magnetic materials, solid solutions of rare earth metals, multiferroics and other solids that are experiencing phase transitions. For professionals in the field of solid state physics and phase transitions.

Abstract Recently NRL researchers have embarked on a basic research effort “Tuning Giant Magnetoelectric Properties in Phase Transformation Multiferroics” focused on multifunctional materials for energy transduction and conversion. Multiferroic materials combine at least two coupled ferroic properties and are used in multiple applications including magnetic field sensors, energy harvesting devices, non-volatile memory and antennas. There are very few single phase multiferroic materials, and they normally have relatively low magnetoelectric (ME) coupling coefficient. In contrast, engineered materials such as ME composites fabricated from piezoelectric and magnetostrictive materials can show multiple orders of magnitudes increase in the ME coupling coefficient. The optimal design of ME composites would lead to conditions of maximum response (strain, induced voltage, or field) with minimum applied electric or magnetic fields, providing advanced materials for transduction, sensing, energy harvesting and other applications. That is why NRL researchers are working on piezoelectric materials with enhanced properties due to a phase transformation that would minimize the stimuli needed to achieve large strains. Key to the successful design and fabrication of ME composites is an understanding of interface characteristics as well as individual material components. In this paper we will review the current status of work at NRL on engineered multiferroic composites comprised of piezoelectric and magnetostrictive materials coupled through strain. There are still many open questions about the interfacial properties as well as the individual component materials. Details will be presented from recent work on material characterization under repetitive cycling, interface characteristics, and stress/electric/thermal effects on driving the phase transition in a relaxor ferroelectric single crystal.