Multiferroic thin-film heterostructures have attracted a great deal of attention due to the increasing demand for novel energy-efficient micro/nano-electronic devices. Both single phase multiferroic materials like BiFeO3 (BFO) thin films, and strain-mediated magnetoelectric (ME) nanocomposites, have the potential to fulfill a number of functional requirements in actual applications—principally, direct control of magnetization by the application of an electric field (E) and vice-versa. From the perspective of material science, however, it is essential to develop a fuller understanding of the complex fabrication-structure-property triangle relationship for these multiferroic thin films. Pulsed laser deposition (PLD) was used in this study to fabricate diverse epitaxial thin film heterostructures on top of single crystal substrates. The crystal structure, phase transition processes (amongst nanodomain distributions, dielectric phases, magnetic spin states, etc.), and various ME-related properties were characterized under different E or temperature environments. Resulting data enabled us to determine the structure-property relationships for a range of multiferroic systems. First, BFO-based heterostructures were studied. Epitaxial BFO thin films were deposited on top of (001)-oriented Pb(Mg1/3Nb2/3)O3-30PbTiO3 (PMN-30PT) single crystal substrates. The strain states of BFO and crystal structural phases were tunable by E applied on the PMN-30PT via both the in-plane and out-of-plane modes. The strain-mediated antiferromagnetic state changes of BFO were also studied using neutron diffraction spectroscopy under E. Then, CoFe2O4(CFO)/tetragonal BFO nanocomposites were successfully fabricated on top of (001)-oriented LaAlO3 single crystal substrates. The surface morphology, crystal structure, magnetic properties, and ME effects were evaluated and compared with CFO/rhombohedral BFO nanocomposites. To enhance the performance of ME heterostructures with PMN-PT substrates, PMN-30PT single crystals with nanograted electrodes were also studied, which evidenced an enhancement in piezoelectric properties and dielectric constant by 36.7% and 38.3%, respectively. X-ray diffraction reciprocal space mapping (RSM) was used to monitor E-induced changes in the apparent symmetry and domain distribution of near-surface regions for the nanograted PMN-30PT crystals. Finally, in order to add antiferroelectric thin films to the family of strain-mediated multiferroic nanocomposites, epitaxial antiferroelectric thin films were prepared. Epitaxial (Pb0.98La0.02)(Zr0.95Ti0.05)O3 (PLZT) thin films were deposited on differently oriented SrTiO3 single crystal substrates. A thickness dependent incommensurate/commensurate antiferroelectric-to-ferroelectric phase transition was identified. The crystal structure, phase transition characteristics and pathways, and energy storage behaviors from room temperature to 250 ℃ were studied, enabling a more systematic understanding of PLZT-based AFE epitaxial thin films. To summarize, a range of epitaxial thin films were prepared using PLD, whose crystal structures and multiferroic properties were related through the strain. Accordingly, properties such as dielectricity, antiferroelectricity, and antiferromagnetism could be adjusted by E. This study sheds further light on the potential for designing desirable strain-mediated multiferroic nano-/micro-devices in the future. / Doctor of Philosophy / As a general definition, the class of materials known as multiferroics possess more than one ferroic order parameter. Multiferroic thin-film heterostructures have attracted a great deal of attention due to the increasing demand for novel energy-efficient micro/nano-electronic devices. Both single phase multiferroic materials like BiFeO3 (BFO) thin films and strain-mediated magnetoelectric (ME) nanocomposites show significant potential for use in next-generation devices due to the fact that one can control magnetic properties via the application of an electric field (E) and vice-versa. From the perspective of material science, however, it is essential to develop a fuller understanding of the complex fabrication-structure-property triangle relationship for these multiferroic thin films. In this study, diverse epitaxial thin film heterostructures were fabricated on top of single crystal substrates. The crystal structure, phase transition processes (amongst nanodomain distributions, dielectric phases, magnetic spin states, etc.), and various ME-related properties were characterized under different E or temperature environments. Resulting data enabled us to determine the structure-property relationships for a range of multiferroic systems. First, BFO-based heterostructures were studied. Epitaxial BFO thin films were deposited on top of (001)-oriented Pb(Mg1/3Nb2/3)O3-30PbTiO3 (PMN-30PT) single crystal substrates. The strain states of BFO and crystal structural phases were tunable by E applied on the PMN-30PT via both the in-plane and out-of-plane modes. The strain-mediated antiferromagnetic state changes of BFO were studied using powerful neutron diffraction spectroscopy under E. Then, CoFe2O4(CFO)/tetragonal BFO nanocomposites were successfully fabricated on top of (001)-oriented LaAlO3 single crystal substrates. The surface morphology, crystal structure, magnetic properties, and ME effects were discussed and compared with CFO/rhombohedral BFO nanocomposites. To enhance the performance of ME heterostructures with PMN-PT substrates, PMN-PT single crystals with nanograted electrodes were also studied, which evidenced an enhancement in piezoelectric properties and dielectric constant by 36.7% and 38.3%, respectively. X-ray diffraction reciprocal space mapping (RSM) technique was used to monitor E-induced changes in the apparent symmetry and domain distribution of near-surface regions for nanograted PMN-PT crystals. Finally, in order to add antiferroelectric thin films to the family of strain-mediated multiferroic nanocomposites, epitaxial antiferroelectric thin films were prepared. Epitaxial (Pb0.98La0.02)(Zr0.95Ti0.05)O3 (PLZT) thin films were deposited on differently oriented SrTiO3 substrates. A thickness dependent incommensurate antiferroelectric-to-ferroelectric phase transition was identified. The crystal structure, phase transition characteristics and pathways, and energy storage behaviors from room temperature to 250 ℃ were studied, enabling a more systematic understanding of PLZT-based AFE epitaxial thin films. To summarize, a range of epitaxial perovskite thin films were prepared, whose crystal structures and multiferroic properties were related through the strain. Accordingly, the properties such as dielectricity, antiferroelectricity, and antiferromagnetism could be adjusted by E. This study sheds further light on the potential for designing desirable strain-mediated multiferroic nano-/micro-devices in the future.

The structural chemistry and magnetic properties of compounds isostructural with La₁₈Li₈Rh₅O₃₉ have been studied. In this cubic structure (space group Pm^{^_}<sub style='position: relative; left: -.5em;'>3</sub>n), [111] chains of alternating RhO₆ octahedra (2a, 8e sites) and LiO₆ trigonal prisms (16i site) occupy channels within a La-O framework. In order to study the consequences of both reducing the dimensions of the channels and introducing paramagnetic cations into both the framework and the polyhedral chains, compositions in the series Nd₁₈Li₈Rh_5-xFe_xO₃₉ (1 &le; x &le; 4) have been synthesised and characterised by magnetometry, neutron diffraction and Mössbauer spectroscopy. Iron preferentially occupies the 2a site as low-spin Fe(IV) and the larger 8e site as high-spin Fe(III). Compositions having x > 1 show spin-glass-like behaviour below ~5 K. The behaviour of this series of compositions has been compared with that of the known series La₁₈Li₈Rh_5-xFe_xO₃₉. In order to facilitate this comparison, the structure of La₁₈Li₈Fe₅O₃₉ has been fully characterised by both neutron diffraction and EXAFS. The use of both techniques has revealed differences between the mean and local environments of iron. In order to explore and extend the range and combinations of elements that can be accommodated in this structure, the Ti-containing compounds Ln₁₈Li₈M₄TiO₃₉ (Ln=La,Nd,Pr,Sm; M=Rh,Fe,Co) have been synthesised. Nd₁₈Li₈Fe₄TiO₃₉ was selected for a detailed study by magnetometry, neutron diffraction, Mössbauer spectroscopy and XANES. Cations were found to be stabilised in unusual oxidation states and disordered over three sites of the Nd₁₈Li₈Fe₄TiO₃₉ polyhedral chains. The 8e site is occupied by high-spin Fe³⁺, Ti³⁺ and Li⁺ in a ratio of 76:20:4; the 2a site by low-spin Fe⁴⁺ and Ti⁴⁺ in a ratio of 79:21 and the trigonal-prismatic 16i site by Li⁺ and Fe³⁺ in a ratio of 98:2. Nd₁₈Li₈Fe₄TiO₃₉ undergoes a transition to a spin-glass state at 4.25(5) K, whereas La₁₈Li₈Fe₄TiO₃₉ revealed a different type of magnetic transition at ~8 K. The nature of this transition is not yet clear. Monophasic samples could not be prepared in the Nd/Rh system and cation vacancies were found in Nd/Co. No pure samples of Sm-containing compositions could be prepared, while the only Pr composition which was obtained pure, according to X-ray diffraction, Pr₁₈Li₈Co₄TiO ₃₉ shows the similar magnetic properties to Pr₁₈Li₈Co₃TiO₃₉. The compositions Ln₁₈Li₈M₃ M'O₃₉ (Ln=La,Nd,Pr,Sm; M,M'=Fe,Co,Ti) with 25% of the 8e sites vacant have been investigated. The Co-containing compositions Nd₁₈Li₈Co₃FeO_39-y, Nd₁₈Li₈CoFe₃O_39-y and Nd₁₈Li₈Co₃TiO_39-y were characterised by neutron diffraction. Cation vacancies on the 8e sites were found to coexist with anion vacancies around the 2a sites. The remaining octahedral sites are occupied by a disordered arrangement of transition-metal cations. The trigonal-prismatic sites are fully occupied by Li except in the case of Nd₁₈Li₈CoFe₃O_39-y where some Fe is present, as confirmed by Mössbauer spectral data. Antiferromagnetic interactions are present on the Nd sublattice in each composition, but a spin glass forms below 5 K when a high concentration of spins is also present on the octahedral sites. The magnetic character of the Ln cations plays an important role in determining the properties of these compounds. Long-range magnetic order of the transition-metal cations was not observed in any compositions. Although this might be partly attributable to the cation disorder in the polyhedral chains, the apparent antiferromagnetic behaviour of Nd-containing compositions in which the transition metals have a low magnetic moment, e.g. Nd₁₈Li₈Co₃TiO_39-y, and the marked contrast between certain La and Nd compositions in which the transition metal content is the same, e.g. Nd₁₈Li₈Fe₄TiO₃₉ and La₁₈Li₈Fe₄TiO₃₉, suggests that the Ln sublattice is fully involved in determining the magnetic behaviour.

Neste trabalho foram produzidos filmes finos de Si[100]/buffer/NiFe/FeMn/Ta (buffer = Cu; Ta) e válvulas de spin de Si[100]/Cu/NiFe/Cu/NiFe/FeMn/Ta via Sputtering, e seus comportamentos magnéticos foram estudados analisando curvas de inversão de primeira ordem (First Order Reversal Curves, FORCs). Um Modelo de Preisach com Exchange-Bias foi desenvolvido e sua implementação computacional permitiu simular a histerese e as curvas forcas das bicamadas de NiFe/FeMn. O modelo também permitiu reproduzir os comportamentos assimétricos dos dois ramos da curva de histerese destes filmes. A análise dos resultados evidenciou os efeitos de campo médio sobre a camada de Py em função da espessura da camada de FeMn. A aplicação da análise FORC nas válvulas de spin se revelou interessante para estudar o grau de acoplamento entre as camadas livre e pressa, assim como os efeitos de campo médio em cada camada. / In this work, thin films of Si[100]/buffer/NiFe/FeMn/Ta (buffer = Cu; Ta) and spin valves of Si[100]/Cu/NiFe/Cu/NiFe/FeMn/Ta were produced via sputtering and their magnetic behavior were studied by First Order Reversal Curves (FORC\'s) analysis. A Preisach Model with Exchange-Bias was developed and applied in order to simulate the hysteresis and the first order reversal curves of the NiFe/FeMn bilayers. In addition, the model allowed to reproduce the asymmetric behaviors present in both branches of the hysteresis curve in these films. The study put in evidence the mean field effects on de Py layer as a function of the thickness of the FeMn layer. The application of the FORC analysis in the spin valves was interesting to study the degree of coupling between the free and the pressed layers, as well as the effect of mean field in each layer.

Medidas de atenuação ultrassônica e constante elástica em ligas de Cr-V, utilizando técnicas de pulso eco foram realizadas e as transições na temperatura de Neel, TN, estudadas. Um modelo teórico é proposto para descrever os comportamentos da atenuação e constante elástica perto da transição em TN. De acordo com o modelo proposto a adição de vanádio diminui drasticamente o coeficiente de difusão, modificando a natureza da transição. Foram utilizadas amostras de cromo contendo 0,2%V; 0,5%V; 0,67%V; 1,0%V e 1,5%V. A partir da dependência aproximadamente linear de TN com a concentração de vanádio conclui-se que 3,3% V corresponderá à TN= 0K. O efeito do campo magnético até 4,5T revelou-se insuficientemente para a obtenção de monodomínio magnético e não causa nenhuma variação mensurável em TN / Measurements of ultrasonic attenuation and elastic Constant in Cr-V alloys, using pulse echo techniques were realized and the transitions at the Neel temperature, TN, were studied. We propose a theoretical model which describe the behavior of the ultrasonic attenuation and elastic Constant near the transition in TN. According to the theoretical model the addition of Vanadium to chromium, drastically diminishes the diffusion coefficient thus changing the nature of the transition. It was used samples of chromium containing 0,2%V; 0,5%V; 0,67%V; 1,0%V and 1,5%V. From the approximately linear dependence of TN with the vanadium concentration it was concluded that 3,3%V corresponds to TN= 0. The effect of magnetic fields up to 4,5T was insufficient to produce single-Q samples, and did not cause any mensurable variation in TN

Neste trabalho foram produzidos filmes finos de Si[100]/buffer/NiFe/FeMn/Ta (buffer = Cu; Ta) e válvulas de spin de Si[100]/Cu/NiFe/Cu/NiFe/FeMn/Ta via Sputtering, e seus comportamentos magnéticos foram estudados analisando curvas de inversão de primeira ordem (First Order Reversal Curves, FORCs). Um Modelo de Preisach com Exchange-Bias foi desenvolvido e sua implementação computacional permitiu simular a histerese e as curvas forcas das bicamadas de NiFe/FeMn. O modelo também permitiu reproduzir os comportamentos assimétricos dos dois ramos da curva de histerese destes filmes. A análise dos resultados evidenciou os efeitos de campo médio sobre a camada de Py em função da espessura da camada de FeMn. A aplicação da análise FORC nas válvulas de spin se revelou interessante para estudar o grau de acoplamento entre as camadas livre e pressa, assim como os efeitos de campo médio em cada camada. / In this work, thin films of Si[100]/buffer/NiFe/FeMn/Ta (buffer = Cu; Ta) and spin valves of Si[100]/Cu/NiFe/Cu/NiFe/FeMn/Ta were produced via sputtering and their magnetic behavior were studied by First Order Reversal Curves (FORC\'s) analysis. A Preisach Model with Exchange-Bias was developed and applied in order to simulate the hysteresis and the first order reversal curves of the NiFe/FeMn bilayers. In addition, the model allowed to reproduce the asymmetric behaviors present in both branches of the hysteresis curve in these films. The study put in evidence the mean field effects on de Py layer as a function of the thickness of the FeMn layer. The application of the FORC analysis in the spin valves was interesting to study the degree of coupling between the free and the pressed layers, as well as the effect of mean field in each layer.

Abstract not available

Il sera question dans ce mémoire de maîtrise de l’étude d’une nouvelle classification des états solides de la matière appelée isolant topologique. Plus précisément, nous étudierons cette classification chez le composé demi-Heusler GdBiPt. Nous avons principalement cherché à savoir si ce composé ternaire est un isolant topologique antiferromagnétique. Une analyse de la susceptibilité magnétique ainsi que de la chaleur spécifique du maté- riau montre la présence d’une transition antiferromagnétique à 8.85(3) K. Une mesure d’anisotropie de cette susceptibilité montre que les plans de spins sont ordonnés sui- vant la direction (1,1,1) et finalement des mesures de résistivité électronique ainsi que de l’effet Hall nous indiquent que nous avons un matériau semimétallique lorsque nous sommes en présence d’antiferromagnétisme. Présentement, les expériences menées ne nous permettent pas d’associer cet état métallique aux états surfaciques issus de l’état d’isolant topologique. / In this thesis will be discussed the study of a new way of characterizing state of matter called a topological insulator. We have mainly investigated whether the ternary compound GdBiPt, from the family of half-Heusler compounds, is an antiferromagnetic topological insulator. An analysis of the magnetic susceptibility and the specific heat of the material shows the presence of an antiferromagnetic transition at 8.85(3) K. A measurement of the anisotropy of the susceptibility shows that plan of spins are ordered according to the crystalline direction (1,1,1) and finally, measurements of electronic re- sistivity and Hall effect indicate that we have a semimetallic material when we are in the presence of antiferromagnetism. At the present, these experiments do not allow us to as- sociate this metallic state with the surface states associated with the topological insulator state of matter.

This thesis presents the NMR measurements on the single crystals LiMnPO4 and Li0.9FeAs. Therefore, the thesis is divided into two separated sections. The first part reports on the competitive next generation cathode material LiMnPO4 with a stable reversible capacity up to 145 mAh/g and a rather flat discharge voltage curve at 4.1 V. For the basic understanding of the material the magnetic properties have been investigated by a Li and P NMR study in the paramagnetic and antiferromagnetic phase. LiMnPO4 shows a strong anisotropy of the dipolar hyperfine coupling due to the strong local magnetic moments at the Mn site. The corresponding dipole tensor of the Li- and P-nuclei is fully determined by orientation and temperature dependent NMR experiments and compared to the calculated values from crystal structure data. Deviations of the experimentally determined values from the theoretical ones are discussed in terms of Mn disorder which could have an impact on the mobility of the Li ions. The disorder is corroborated by diffuse x-ray diffraction experiments which indicate a shift of the heavy elements in the lattice, namely the Mn atoms. Furthermore, the spin arrangement in the relative strong field of 7.0494 T in the antiferromagnetic state is understood by the NMR measurements. In order to obtain parameters of the Li ion diffusion in LiMnPO4 measurements of the spin lattice relaxation rate were performed. Due to the strong dipolar coupling between the Li-nuclei and the magnetic moments at the Mn site it is difficult to extract parameters which can characterize the diffusive behavior of the Li ions. The second section reports on the AC/DC susceptibility and NMR/NQR studies on Li deficit samples labeled as Li0.9FeAs. LiFeAs belongs to the family of the superconducting Pnictides which are discovered in 2008 by H. Hosono et al. In recent studies the stoichiometric compound reveals triplet superconductivity below Tc ∼ 18 K which demands ferromagnetic coupling of the electrons in the Cooper pairs. In Li0.9FeAs the Li deficit acts like hole doping which suppresses the superconductivity. Then ferromagnetism can arise which is very interesting because of the vicinity to the triplet superconductivity. With the microscopic methods NMR/NQR on the Li and As nuclei, it was investigated where the ferromagnetism can be located in Li0.9FeAs. Recent susceptibility, ESR and µSR studies reveal an internal field due to the ferromagnetism. In contrast, the internal field could not be used to perform zero field NMR measurements. Possible reasons for this discrepancy are discussed. In addition, the automatic insitu AC susceptibility technique by using the NMR radio frequency circuit has been tested by a reference compound Co2TiGa which shows itinerant ferromagnetism. Similar curves are observed for Li0.9FeAs which indicate the existence of itinerant magnetic moments in Li0.9FeAs. Furthermore, in order to determine the size of the dipolar contribution from the magnetic moments of the Fe the dipolar hyperfine coupling tensor was calculated from the crystal structure data. The comparison of the experimental and calculated hyperfine coupling elements reveals transferred hyperfine fields in LiFeAs.

[Truncated abstract] Although exchange bias was discovered more than four decades ago, a satisfactory understanding of every instance of exchange bias observed in experiment has not yet emerged. Understanding exchange bias is complicated by many factors. For example, details of the antiferromagnet interface structure set up during the initial field cooling, thermal activation processes in the ferromagnet and antiferromagnet, and domain formation and domain wall movement in the antiferromagnet are all important in determining features associated with exchange bias. Two exchange bias systems are investigated in this thesis. One is a disordered system: a single layer Co/CoO film with random interfaces prepared by a reactive RF sputtering technique. The other is a ‘model’ system of Fe/KFeF 3 bilayers with compensated interfaces prepared by molecular beam epitaxy (MBE). The central theme of this work is to understand exchange bias and other related magnetic properties in these two very different systems. The Co/CoO exchange bias system studied here is different in structure from conventional exchange bias systems such as bilayer and multilayer systems where interfaces between ferromagnet and antiferromagnet are reasonably well defined. In this Co/CoO system, the Co and CoO is in the form of particles distributed randomly in a sputtered film. The interfaces between the Co and CoO are randomly distributed and may not be continuous over a large length scale. More importantly, the interface area is dependent on the shape and size of the particles and on their distribution. Many unique magnetic properties are related to the random interface in this system. For example, exchange bias and coercivity obtained at low temperatures are very large due to the large interface area between Co and CoO particles. The interface area can be controlled by changing the Co/CoO mass ratio in the film. Unlike in bilayer systems, film thickness in this single layer Co/CoO system turns out not to be critical for exchange bias and coercivity. The independence of film thickness may be technically important. More interestingly, because the interface is random, exchange bias can be setup by field cooling in any direction. Both training and magnetic viscosity effects were studied and provided evidence of thermal activation processes in this Co/CoO system. Training is explained as formation of a domain wall in the CoO with motion limited locally due to limited continuity of Synthesis and Characterization of Magnetic Thin Films - Exchange Bias Systems interfaces between the Co and CoO. Specific magnetization measurements over time were made and studied using viscosity theory. The magnetic viscosity was found to be strongly temperature dependent. There is a broad distribution of blocking temperatures which might be due to a broad distribution of Co particle sizes

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2009. / Title from title screen (site viewed June 26, 2009). PDF text: xxvii, 209 p. : ill. (some col.) ; 17 Mb. UMI publication number: AAT 3350440. Includes bibliographical references. Also available in microfilm and microfiche formats.