Thèse de doctorat : Physique : Tours : 2008. / Titre provenant de l'écran-titre.

Magnetic oxides exhibit rich complexity in their fundamental physical properties determined by the intricate interplay between structural, electronic and magnetic degrees of freedom. The common themes that are often present in these systems are the phase coexistence, strong magnetostructural coupling, and possible spin frustration induced by lattice geometry. While a complete understanding of the ground state magnetic properties and cooperative phenomena in this class of compounds is key to manipulating their functionality for applications, it remains among the most challenging problems facing condensed-matter physics today. To address these outstanding issues, it is essential to employ experimental methods that allow for detailed investigations of the temperature and magnetic field response of the different phases. In this PhD dissertation, I will demonstrate the relatively unconventional experimental methods of magnetocaloric effect (MCE) and radio-frequency transverse susceptibility (TS) as powerful probes of multiple magnetic transitions, glassy phenomena, and ground state magnetic properties in a large class of complex magnetic oxides, including La0.7Ca0.3-xSrxMnO3 (x = 0, 0.05, 0.1, 0.2 and 0.25), Pr0.5Sr0.5MnO3, Pr1-xSrxCoO3 (x = 0.3, 0.35, 0.4 and 0.5), La5/8−xPrxCa3/8MnO3 (x = 0.275 and 0.375), and Ca3Co2O6. First, the influences of strain and grain boundaries, via chemical substitution and reduced dimensionality, were studied via MCE in La0.7Ca0.3-xSrxMnO3. Polycrystalline, single crystalline, and thin-film La0.7Ca0.3-xSrxMnO3 samples show a paramagnetic to ferromagnetic transition at a wide variety of temperatures as well as an observed change in the fundamental nature of the transition (i.e. first-order magnetic transition to second order magnetic transition) that is dependent on the chemical concentration and dimensionality. Systematic TS and MCE experiments on Pr0.5Sr0.5MnO3 and Pr0.5Sr0.5CoO3 have uncovered the different nature of low-temperature magnetic phases and demonstrate the importance of coupled structural/magnetocrystalline anisotropy in these half-doped perovskite systems. These findings point to the existence of a distinct class of phenomena in transition-metal oxide materials due to the unique interplay between structure and magnetic anisotropy, and provide evidence for the interplay of spin and orbital order as the origin of intrinsic phase separation in manganites. While Pr0.5Sr0.5MnO3 provides important insights into the influence of first- and second-order transitions on the MCE and refrigerant capacity (RC) in a single material, giving a good guidance on the development of magnetocaloric materials for active magnetic refrigeration, Pr1-xSrxCoO3 provides an excellent system for determining the structural entropy change and its contribution to the MCE in magnetocaloric materials. We have demonstrated that the structural entropy contributes significantly to the total entropy change and the structurally coupled magnetocrystalline anisotropy plays a crucial role in tailoring the magnetocaloric properties for active magnetic refrigeration technology. In the case of La5/8−xPrxCa3/8MnO3, whose bulk form is comprised of micron-sized regions of ferromagnetic (FM), paramagnetic (PM), and charge-ordered (CO) phases, TS and MCE experiments have evidenced the dominance of low-temperature FM and high-temperature CO phases. The "dynamic" strain liquid state is strongly dependent on magnetic field, while the "frozen" strain-glass state is almost magnetic field independent. The sharp changes in the magnetization, electrical resistivity, and magnetic entropy just below the Curie temperature occur via the growth of FM domains already present in the material, even in zero magnetic field. The subtle balance of coexisting phases and kinetic arrest are also probed by MCE and TS experiments, leading to a new and more comprehensive magnetic phase diagram. A geometrically frustrated spin chain compound Ca3Co2O6 provides an interesting case study for understanding the cooperative phenomena of low-dimensional magnetism and topological magnetic frustration in a single material. Our MCE studies have yielded new insights into the nature of switching between multi-states and competing interactions within spin chains and between them, leading to a more comprehensive magnetic phase diagram.

Tirta ErMnO3 optinės savybės: apskaičiuotos dielektrinių skvarbų spektrinės priklausomybės, optinių šuolių energijos, lūžio ir sugerties rodikliai. Tyrimai atlikti elipsometru, dielektrinė funkcija apskaičiuojama pagal vienašio kristalo modelį. / Manganites have attracted a lot of attention due to their magnetical properties: colossal magnetoresistance, variety of phase, but the optical properties of ErMnO3 were not widely investigated. Investigation of optical properties of ErMnO3 single crystal were studie by means of ellipsometry method. Ellipsometric studies have been carried out in the spectral range of 1- 5 eV. The photimetric ellipsometer with rotating analyzer was used. Experimental ellipsometer data were analysed in the isotropical and uniaxial crystal models. The optical properties of ErMnO3 were investigated: ellipsometric parameters Ψ and Δ were determinated, the components of dielectric function and energy of optical transition were found, calculated refractive and absorption indexs.

Disertacijoje nagrinėjamos įvairios galimybės panaudoti feromagnetinių oksidų – manganitų sluoksnius bei jų darinius naujų spintronikos prietaisų gaminimui. Šio darbo pagrindiniu tyrimo objektu pasirinktos sandūros, sudarytos tarp dvivalenčiais (Ca, Ba, Sr) ir keturvalenčiais (Ce) jonais legiruotų lantano mangano oksidų plonųjų sluoksnių, o taip pat tarp manganitų ir elektroninio laidumo SrTiO3<Nb> (STON) bei n - Si padėklų. Darbe pateiktas išsamus minėtų manganitų sluoksnių ir jų darinių gaminimo magnetroninio dulkinimo ir impulsinio lazerinio garinimo būdais aprašymas. Disertacijoje pateikti plonųjų manganitų sluoksnių, užaugintų ant skirtingų padėklų, kristalinės struktūros bei paviršiaus kokybės tyrimo duomenys, aprašytas magnetiniu lauku valdomų diodinių darinių formavimas, jų elektrinių bei magnetinių savybių tyrimai, įvertinti svarbiausi atskirų manganitų sluoksnių bei jų diodinių darinių elektrofiziniai parametrai. Atlikus kompleksinius keturvalenčiais Ce4+ jonais legiruotų lantano manganito sluoksnių kristalinės sandaros bei elektrinių savybių tyrimus nustatyta, kad šie sluoksniai pasižymi ne elektroniniu, kaip buvo skelbta anksčiau, o skyliniu elektriniu laidumu. Skylinis junginio elektrinis laidumas paaiškintas nežymiu šalutinės CeO2 fazės ir katijonų vakansijų susidarymu auginamuose sluoksniuose. Pateikti Ca, Ba, Sr ir Ce jonais legiruotų manganitų įvairialyčių darinių palyginamieji tyrimai, įvertinta padėklo įtaką kristalinės manganitų sandaros tobulumui... [toliau žr. visą tekstą] / In this dissertation application of the lanthanum manganite films and their heterostructures for fabrication of new spintronic devices is discussed. The main subjects of this work are the junctions between lanthanum manganite oxide thin films doped by divalent (Ca, Ba, Sr) and tetravalent (Ce) ions as well heterojunctions formed between lanthanum manganites and n-type SrTiO3<Nb> (STON) or n - Si substrates. The influence of doping and substrate influence on crystalline quality of manganite film structures, interface roughness as well as their electrical and magnetic properties has been estimated in this dissertation. After performing complex investigations it has been determined that tetravalent Ce ion doped lanthanum manganite films have not the electron but hole-type conductivity on the contrary to that has been reported earlier. Forming of magnetic filed dependent “manganite / (STON, n - Si)“ diode structures has been described, comparative studies of electrical and magnetic properties have been presented, and major electro-physical parameters have been estimated in this work. Possible reasons of the origin of positive and negative magnetoresistance have been pointed out. In addition, structural stabilization problems of BiFeO3 compound, exhibiting at the same time magnetic as well as ferroelectric properties and possibilities of application of its unique properties in various lanthanum manganite structures for the development of new magnetic and electrical filed... [to full text]

In this dissertation application of the lanthanum manganite films and their heterostructures for fabrication of new spintronic devices is discussed. The main subjects of this work are the junctions between lanthanum manganite oxide thin films doped by divalent (Ca, Ba, Sr) and tetravalent (Ce) ions as well heterojunctions formed between lanthanum manganites and n-type SrTiO3<Nb> (STON) or n - Si substrates. The influence of doping and substrate influence on crystalline quality of manganite film structures, interface roughness as well as their electrical and magnetic properties has been estimated in this dissertation. After performing complex investigations it has been determined that tetravalent Ce ion doped lanthanum manganite films have not the electron but hole-type conductivity on the contrary to that has been reported earlier. Forming of magnetic filed dependent “manganite / (STON, n - Si)“ diode structures has been described, comparative studies of electrical and magnetic properties have been presented, and major electro-physical parameters have been estimated in this work. Possible reasons of the origin of positive and negative magnetoresistance have been pointed out. In addition, structural stabilization problems of BiFeO3 compound, exhibiting at the same time magnetic as well as ferroelectric properties and possibilities of application of its unique properties in various lanthanum manganite structures for the development of new magnetic and electrical filed... [to full text] / Disertacijoje nagrinėjamos įvairios galimybės panaudoti feromagnetinių oksidų – manganitų sluoksnius bei jų darinius naujų spintronikos prietaisų gaminimui. Šio darbo pagrindiniu tyrimo objektu pasirinktos sandūros, sudarytos tarp dvivalenčiais (Ca, Ba, Sr) ir keturvalenčiais (Ce) jonais legiruotų lantano mangano oksidų plonųjų sluoksnių, o taip pat tarp manganitų ir elektroninio laidumo SrTiO3<Nb> (STON) bei n - Si padėklų. Darbe pateiktas išsamus minėtų manganitų sluoksnių ir jų darinių gaminimo magnetroninio dulkinimo ir impulsinio lazerinio garinimo būdais aprašymas. Disertacijoje pateikti plonųjų manganitų sluoksnių, užaugintų ant skirtingų padėklų, kristalinės struktūros bei paviršiaus kokybės tyrimo duomenys, aprašytas magnetiniu lauku valdomų diodinių darinių formavimas, jų elektrinių bei magnetinių savybių tyrimai, įvertinti svarbiausi atskirų manganitų sluoksnių bei jų diodinių darinių elektrofiziniai parametrai. Atlikus kompleksinius keturvalenčiais Ce4+ jonais legiruotų lantano manganito sluoksnių kristalinės sandaros bei elektrinių savybių tyrimus nustatyta, kad šie sluoksniai pasižymi ne elektroniniu, kaip buvo skelbta anksčiau, o skyliniu elektriniu laidumu. Skylinis junginio elektrinis laidumas paaiškintas nežymiu šalutinės CeO2 fazės ir katijonų vakansijų susidarymu auginamuose sluoksniuose. Pateikti Ca, Ba, Sr ir Ce jonais legiruotų manganitų įvairialyčių darinių palyginamieji tyrimai, įvertinta padėklo įtaką kristalinės manganitų sandaros tobulumui... [toliau žr. visą tekstą]

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Cette thèse concerne l'étude et la visualisation par imagerie magnéto-optique Kerr à la température ambiante du mode de retournement de l'aimantation au sein de couches minces ferromagnétiques de manganites de composition La0,7Sr0,3MnO3 (LSMO). Au cours du travail de thèse, un banc d'imagerie a été réalisé et une méthode d'imagerie vectorielle de l'aimantation a été proposée. Ce système d'imagerie a été utilisé pour étudier d'une part l'influence du substrat et des contraintes qu'il induit dans la couche mince et d'autre part l'influence de la forme des échantillons, sur le piégeage et le mode de retournement des domaines magnétiques présents dans la couche mince. Dans le cas du substrat LSAT ((LaAlO3)0.3(Sr2AlTaO6)0.7), la compression induite dans la couche mince fait apparaître une composante d'aimantation hors du plan et un plan de facile aimantation sans direction privilégiée dans ce plan. Le retournement des domaines planaires est alors de type cohérent. Dans le cas du substrat STO (SrTiO3), d'orientation (001), l'anisotropie magnétique est biaxiale et le retournement d'aimantation s'opère par nucléation puis propagation de domaines. Dans le cas de substrats vicinaux de STO, l'anisotropie magnétique devient uniaxiale et l'axe de facile aimantation est parallèle aux marches en surface de la couche. Le retournement de domaines se produit par nucléation et propagation dans le cas où le champ magnétique est appliqué parallèlement aux marches du substrat vicinal. Quand le champ magnétique est appliqué perpendiculairement aux marches du substrat vicinal, on assiste à un retournement cohérent des domaines magnétiques. Ces travaux constituent une première étape dans la compréhension et la maîtrise du comportement magnétique de dispositifs spintroniques.

We have investigated several topics in the area of manganites including oxygen disorder, grain boundaries, low field magnetoresistance, magnetoresistive anisotropy and magnetic properties. Studied materials were in the form of polycrystalline samples and epitaxial thin films. The studied compounds were Sm(1-x)Sr(x)MnO3 (SSMO) and La(1-x)Ca(x)MnO3 (LCMO). 1-We have studied the effects of oxygen disorder and grain boundary disorder in the SSMO system close to half hole doping level. The temperature dependencies of resistivity and magnetoresistance were measured as a function of the vacuum annealing time. We observed a logarithmic increase of the resistivity as a function of vacuum annealing time. We have shown that an increasing grain boundary disorder softens the magnetic phase transition from a first order phase transition into a second order transition. Furthermore, the peaks in the resistivity and specific heat are broadened and there is an increase in the charge-carrier scattering rates in the metallic state. On the other hand, the polaronic hopping activation energies in the insulating state changed slightly as a function of grain boundary disorder. The origin of these phenomena is discussed. Magnetoresistive anisotropy has been studied as a function of the grain size. Results showed a strong grain size dependence of anisotropic electrical transport in granular samples of manganites. 2-We investigated the anisotropic magnetoresistance (AMR) in ultrathin LCMO films grown on various substrates. It was found that depending on the strain state, the AMR in some of these systems exceeds 100% and can even change sign. These changes are dramatic when compared to the few percent change in AMR in conventional ferromagnets. The mechanism behind these changes in the AMR is discussed. We have also studied the effects of strain on resistive peak broadening with a simple percolation model. We have shown that strain associated with a lattice mismatched substrate in thin films can cause new electronic behavior, not found in bulk materials or thicker films of the same chemical composition. Resistivity of the ultra thin films exhibit strong relaxation effects when measured as a function of time in a constant magnetic field.

In this work, the effect of reversible elastic lattice strain on the electronic properties of a) (Pr1−y Lay )0.7 Ca0.3 MnO3 (PLCMO) thin films and b) the interface layer of La0.7 Sr0.3 MnO3 (LSMO) with SrTiO3 (STO) has been determined using piezoelectric substrates. Lattice strain is known to effectively alter the electronic structure of compounds from the manganite family, since it shifts the balance of competing electronic interactions by changing bond angles and bond lengths.The PLCMO films have been repared by pulsed laser deposition (PLD) from a La0.7 Ca0.3 MnO3 (LCMO) and a Pr0.7 Ca0.3 MnO3 (PCMO) target. The metal- insulator phase boundary has been established to lie around y = 0.6. In films with y = 0.6, the piezoelectric release of tensile strain in the film plane induces a drastic reduction of the resistance, or a “colossal” elastoresistance. Resistive gauge factors as high as Γ = 1000 have been found. Consistent with the transport results, the release of tensile strain leads to an increase in both the Curie temperature and the magnetisation. The coexistence of the ferromagnetic metallic (FMM) and charge ordered insulating (COI) phases in PLCMO has been found to be strongly affected by the reversible substrate strain. Both the magnetisation and the resistance data in controlled strain states demonstrate a strong suppression of the ferromagnetic double exchange interaction by tensile strain. [La0.7 Sr0.3 MnO/SrTiO3 ] superlattices have been deposited on STO and piezoelectric PMN-PT (001) (PbMg1/3 Nb2/3 O3 )0.72 (PbTiO3 )0.28 substrates by PLD. X-ray reflectivity (XRR) measurements show clear Kiessig fringes as well as the larger interference maxima caused by the superlattice, giving qualitative proof of a well defined superlattice structure with sharp interfaces on both substrates. With decreasing LSMO layer thickness d, the samples show a sharp decrease of the Curie temperature, accompanied by a decrease of the saturation magnetisation and an increase of the coercive field around d = 5 nm. Reversible strain measurements on thicker superlattices (d = 16.7 nm) reveal a behaviour of the magnetisation similar to that of single thick films of LSMO. When d is decreased, the strain induced relative change in magnetisation ∆M/M0 shows a behaviour comparable to PLCMO thin films. This has been attributed to the increased volume fraction of the LSMO inter- face layer with STO, which displays a reduced magnetic order and phase-separated tendencies. From the absolute change in magnetisation per interface, the thickness of the so-called magnetically “dead” layer of the LSMO has been estimated to lie between 1.3 nm and 1.7 nm in the superlattices grown on PMN-PT.

Orientador: Paulo Noronha Lisboa Filho / Banca: José Varalda / Banca: José Humberto Dias da Silva / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: As manganitas óxidas apresentam um complexo diagrama de fases magnéticas e muitos dos seus mecanismos fundamentais de interação magnética ainda precisam ser explorados. A nível cristalográfico, as manganitas óxidas de terras-raras têm suas propriedades magnéticas fortemente afetadas pela variação do íon de terra na estrutura cristalina do composto, pela natureza do elemento de transição presente na composição e pela possibilidade deste metal sofrer flutuações de valência. Além disso, a natural ocorrência de vacâncias de oxigênio também presentes nesses materiais cerâmicos são responsáveis por respostas magnéticas distintas. Este trabalho teve como objetivo a síntese, a caracterização estrutural e a caracterização magnética de dois conjuntos de amostras policristalinas da família Er'Co IND. x''Mn IND. 1-x''O IND> 3+ou - δ' preparados pelo Método dos Precursores Poliméricos. O primeiro conjunto apresenta diferentes valores das composições relativas de manganês e cobalto e um segundo conjunto apresenta variações na estequiometria de oxigênio, além dos compostos base ErMn'O POT. 3' e ErCo'O POT. 3'. Para a caracterização cristalográfica, as amostras foram estudadas por difração de Raios X e analisadas através do método de refinamento Rietveld, e a caracterização magnética foi feita por medidas de magnetização em função da temperatura e em função do campo magnético aplicado. Da análise estrutural, tem-se que as amostras produzidas possuíam frações muito pequenas de fases secundárias, sendo que as fases foram quantificadas através do método Rietveld. As medidas magnéticas mostraram a extensa coexistência de diferentes respostas magnéticas para as amostras com composição relativa Co/Mn. / Abstract: Manganese based oxides present a very complex magnetic phase diagram and still have many of their basic physical properties and magnetic interaction to be better explored. At crystallographic level, rare-earth oxide manganites have their magnetic properties strongly effected by tchanges in the rare-earth ion present in the structure, the nature of the transition element in the structure and also by the possibility of electronic valence fluctuations. Furthermore, the occurrence of oxygen vacancies are also responsible for a sort of different magnetic responses. In this work it was studied the synthesis procedure, structural and magnetic characterization of polycrystalline samples of the ErMn'O POT. 3' e ErCo'O POT. 3' family prepared by a polymeric precursors method. A first group of samples presents different manganese and cobalt contents ratio and a second group of the analized samples presents variations in the oxygen stoichiometric. The structural and crystalographic characterization were performed by X ray powder diffraction and further analyzed by the Rietveld refinement method, and the magnetic characteristic were studied by measurements of magnetization as a function of temperature at different values of applied magnetic field. From structural analysis, the produced sample have a small piece of secondary phase, that were quantifity using the Rietveld method. The magnetic measures showed a larger coexistence of differents magnetics interactions to sample with relative composition Co/Mn. / Mestre