Orientadora: Profa. Dra. Raquel de Almeida Ribeiro / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Física, 2017. / Em Física da Matéria Condesada, as terras raras apresentam um papel importante em várias aplicações tecnológicas. Suas camadas 4f incompletas possuem enumeras con- gurações diferentes possibilitando o desenvolvimento e melhoramento de propriedades interessantes. Materiais supercondutores, lasers de estado sólido, radares e ímãs permanentes são bons exemplos de dispositivos que utilizam materiais desenvolvidos com terras raras. Quando terras raras são colocadas em um material matriz, as interações entre esses elementos ou entre a matriz e as terras raras fazem com que os seus estados eletrônicos mudem. Estruturas cristalinas apresentam campo elétrico cristalino, cuja teoria desenvolvida no século passado foi amplamente estudada e aplicada à vários grupos de simetria em cristais bulk. Até o momento, porém, muito pouco tem sido estudado a respeito de como o campo elétrico de estruturas não convencionais, como quasicristias e nanocristais, afeta os autoestados das terras raras. Portanto, o objetivo desse projeto foi analizar o efeito de campo elétrico cristalino em dois tipos de materiais: Nanopartículas cúbicas com tamanho de 8 nm e quasicristais icosaédricos, bem como seu aproximante. Para isso, nanopartículas de NaY1..xRExF4 (RE = Yb, Er, Dy, Gd) foram sintetizadas pelo método de termo-decomposição e quasicristais de Au-Al-Yb foram crescidos em forno a arco. Para a determinação parâmetros de campo elétrico cristalino Bm n , foram feitos ajustes das curvas de magnetização dependentes da temperatura e do campo magnético aplicado. Além disso, para os quasicristais foi encontrado um grupo de simetria pontual equivalente e seus parâmetros de campo elétrico cristalino foram comparados com os de seus aproximantes. Com isso, observou-se que somente parâmetros de segunda ordem apresentaram uma diferença signicativa quando comparados entre essas duas estruturas; B0 2 é 20 vezes maior para a estrutura quasicristalina. Para as nanopartículas cúbicas, uma Hamiltoniana total foi proposta e com isso foi feita um simulação para determinar a separação total dos níveis de energia da camada incompleta 4f das terras raras. Além disso, o espectro de Up conversion foi medido e comparado com a simulação teórica. A largura de linha do espectro teórico, 470 20 K, para a transição 4S3=2 ! 4I15=2 , é comparável aos resultados empíricos, 650 50 K. O estado fundamental dos sistemas foi conrmado pela técnica de Ressonância Eletrônica de Spin. Dessa forma, foi estabelecida uma realação de como a separação total dos multipletos-J afeta a emissão de Up conversion destas NP's. / In Condensed Matter Physics, rare earth elements play an important role in several technological applications. Their complex 4f unfullled shell presents numerous dierent congurations, making possible to engineer or tune interesting properties. Superconductors, solid state lasers, radars and permanent magnets are some examples of cutting edge devices using materials developed with rare earth elements. When a rare earth ion is placed in a host material, their interactions with each other or with the host lattice are responsible for the arrangement of their electronic state. Crystalline structures exhibit the crystal eld eect, whose theory developed in the last century has been largely applied and studied to various point group symmetries in bulk crystals. However, there is a lack of researches in how the electric eld of non-conventional host lattices, such as quasicrystals and nanocrystals, aect rare earth's eigenstates. Therefore, the aim of this project was to analyze the crystal eld eect in two dierent kind of materials: Cubic nanoparticles with 8 nm in size and icosahedral bulk quasicristals, as well as their crystal approximant. For that, NaY1..xRExF4 (RE = Yb, Er, Dy, Gd) nanoparticles were synthesized by temperature decomposition and Au-Al- Yb quasicrystals were grown by arc-melting. Fittings of the thermal and eld dependent magnetization were used to determine the crystal electric eld parameters Bmn . In the quasicrystal material case, an equivalent point group symmetry was obtained and their crystal electric eld parameters were compared with the ones of their approximant. Only parameters of second order substantially diered between both structures, B02 was found out to be around 20 times larger than that for the approximant. Moreover, in the cubic nanostructures case, the overall splitting of the 4f unfullled shell of the RE elements was determined diagonalizing a proposed total Hamiltonian, whose terms include the Crystal Electric Field parameters. In addition, the up-conversion light emission signal was acquired and compared with a theoretical simulation. The theoretical up-conversion light emission line-width found out as 471 20 K, for the transition 4S3=2 ! 4I15=2 , is comparable to empirical results, 650 50 K. The ground state of the systems was conrmed by Electron Spin Resonance analysis. In this case, a relation with how the overall energy splitting of the J-multiplets aect the UC conversion light emission of theses NP's was established.

Cette thèse se concentre sur l'étude de composés magnétiques géométriquement frustrés où les ions magnétiques se situent aux sommets d'un réseau de tétraèdres partageant leurs sommets: les composés pyrochlores. Deux familles de formule chimique R2M2O7, où R est un lanthanide et M= Ti, Sn, sont particulièrement intéressantes puisqu'elles présentent une grande variété d'états magnétiques exotiques. Premièrement, nous avons étudié le champ cristallin agissant au site de la terre rare dans l'approximation de Stevens où uniquement le terme fondamental est considéré. Un jeu unique de paramètres a été déterminé pour chaque famille considérée grâce à une analyse globale incluant des spectres de neutrons inélastiques de plusieurs composés. Ensuite, nous avons caractérisé avec un large éventail de techniques les propriétés physiques à basse température de Nd2Sn2O7. En dessous de la température de transition Tc=0.91 K, ce composé possède un ordre magnétique à longue portée dans la configuration de spins dite "all-in-all-out". Une persistance de la dynamique de spins a été révélée dans la phase ordonnée, attribuée à des excitations unidimensionnelles de spins. Une dynamique de spins anormalement lente est également reportée dans la phase paramagnétique. Enfin, nous avons apporté quelques informations sur les deux états fondamentaux proposés pour le composé très étudié Tb2Ti2O7: premièrement, l'apparition d'une transition Jahn-Teller à basse température est suggérée mais l'absence d'élargissement des pics de Bragg réfute la présence d'une transition structurale. Enfin ce composé pourrait être un exemple d'une glace de spin quantique mais l'existence d'un plateau d'aimantation n'est pas évident jusqu'à T=20 mK. / This Phd thesis focuses on the study of magnetically frustrated compounds where magnetic ions lie at the vertices of a corner-sharing tetrahedra network: the pyrochlore compounds. The two series of chemical formula R2M2O7, where R is a lanthanide and M=Ti, Sn, are of peculiar interest since they display a large variety of exotic magnetic ground states. First, we have studied the crystal-electric-field acting at the rare earth within the Stevens approximation where only the ground state multiplet is considered. A single set of parameters for each families of interest has been determined through a global analysis including several inelastic neutron scattering spectra of various compounds. Then, we have characterised with a large panel of techniques the low temperature physical properties of Nd2Sn2O7. This compound enters a long-range magnetic order at transition temperature Tc=0.91 K with an ``all-in-all-out'' spin configuration. A persistence of spin dynamics has been found in the ordered phase, ascribed to one-dimensional spin loops excitations. Anomalously slow paramagnetic spin fluctuations are also reported. Finally, we have brought information on the two proposed ground states of the widely studied compound Tb2Ti2O7: first, a Jahn-Teller transition is claimed to occur at low temperatures but no broadening of the Bragg peaks is seen down to T=4 K precluding premises of a structural transition. Secondly, this compound could be a realisation of a quantum spin-ice but no definitive evidence of a magnetisation plateau is found down to T=20 mK.

Cette thèse se concentre sur l'étude de composés magnétiques géométriquement frustrés où les ions magnétiques se situent aux sommets d'un réseau de tétraèdres partageant leurs sommets: les composés pyrochlores. Deux familles de formule chimique R2M2O7, où R est un lanthanide et M= Ti, Sn, sont particulièrement intéressantes puisqu'elles présentent une grande variété d'états magnétiques exotiques. Premièrement, nous avons étudié le champ cristallin agissant au site de la terre rare dans l'approximation de Stevens où uniquement le terme fondamental est considéré. Un jeu unique de paramètres a été déterminé pour chaque famille considérée grâce à une analyse globale incluant des spectres de neutrons inélastiques de plusieurs composés. Ensuite, nous avons caractérisé avec un large éventail de techniques les propriétés physiques à basse température de Nd2Sn2O7. En dessous de la température de transition Tc=0.91 K, ce composé possède un ordre magnétique à longue portée dans la configuration de spins dite "all-in-all-out". Une persistance de la dynamique de spins a été révélée dans la phase ordonnée, attribuée à des excitations unidimensionnelles de spins. Une dynamique de spins anormalement lente est également reportée dans la phase paramagnétique. Enfin, nous avons apporté quelques informations sur les deux états fondamentaux proposés pour le composé très étudié Tb2Ti2O7: premièrement, l'apparition d'une transition Jahn-Teller à basse température est suggérée mais l'absence d'élargissement des pics de Bragg réfute la présence d'une transition structurale. Enfin ce composé pourrait être un exemple d'une glace de spin quantique mais l'existence d'un plateau d'aimantation n'est pas évident jusqu'à T=20 mK. / This Phd thesis focuses on the study of magnetically frustrated compounds where magnetic ions lie at the vertices of a corner-sharing tetrahedra network: the pyrochlore compounds. The two series of chemical formula R2M2O7, where R is a lanthanide and M=Ti, Sn, are of peculiar interest since they display a large variety of exotic magnetic ground states. First, we have studied the crystal-electric-field acting at the rare earth within the Stevens approximation where only the ground state multiplet is considered. A single set of parameters for each families of interest has been determined through a global analysis including several inelastic neutron scattering spectra of various compounds. Then, we have characterised with a large panel of techniques the low temperature physical properties of Nd2Sn2O7. This compound enters a long-range magnetic order at transition temperature Tc=0.91 K with an ``all-in-all-out'' spin configuration. A persistence of spin dynamics has been found in the ordered phase, ascribed to one-dimensional spin loops excitations. Anomalously slow paramagnetic spin fluctuations are also reported. Finally, we have brought information on the two proposed ground states of the widely studied compound Tb2Ti2O7: first, a Jahn-Teller transition is claimed to occur at low temperatures but no broadening of the Bragg peaks is seen down to T=4 K precluding premises of a structural transition. Secondly, this compound could be a realisation of a quantum spin-ice but no definitive evidence of a magnetisation plateau is found down to T=20 mK.

>Magister Scientiae - MSc / The present study investigates the strength of the hybridization by substituting Ce atom in Kondo lattice CeIn3 with Gd, Tb, and Dy and by changing the chemical environment around the Ce atom in substituting Pt with Ni in CePtSi2. This thesis covers four chapters outline as follows: Chapter 1 introduces the theoretical background in rare earths elements, and an overview of the physics of heavy-fermion and Kondo systems. Chapter 2 presents the experimental details used in this thesis. Chapter 3 report the effect of substituting Ce with moment bearing rare-earth elements RE = Gd, Tb and Dy in CeIn3, through x-ray diffraction (XRD) and electrical resistivity measurements

Orientadores: Narcizo Marques de Souza Neto, Flávio Cesar Guimarães Gandra / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-27T10:57:14Z (GMT). No. of bitstreams: 1 Veiga_LarissaSayuriIshibe_D.pdf: 10330689 bytes, checksum: 72bdd1a8fad1f82f880bb2c86fcd6a9e (MD5) Previous issue date: 2015 / Resumo: Este trabalho teve como objetivo a investigação de diversos mecanismos físicos provenientes das estruturas eletrônicas, magnéticas e cristalinas de sistemas ternários de terras raras e metais de transição 3d-5d através do uso das técnicas de espectroscopia de absorção de raios X e difração de raios X sob altas pressões. Dentre os fenômenos físicos estudados em função da compressão da rede cristalina induzida pela aplicação da pressão estão o magnetismo proveniente dos orbitais 4f e 5d nos sistemas ternários RERh4B4 (com RE = Dy e Er), os efeitos do campo elétrico cristalino e as interações de troca magnéticas nas perovskitas duplas 3d-5d (AFeOsO6, com A = Ca e Sr) e o acoplamento spin-órbita nos metais de transição 5d. As propriedades eletrônicas e magnéticas dos orbitais 4f e 5d das terras raras nos compostos da família RERh4B4 (RE = Dy e Er) foram investigadas através de experimentos de XANES e XMCD sob altas pressões na borda L3 do Dy e Er . Os sinais magnéticos das contribuições quadrupolar (2p3/2-> 4f) e dipolar (2p3/2->5d) presentes nos espectros de XMCD, em ambos os compostos, diminuem progressivamente em função da pressão. Este comportamento foi explicado em termos das interações de troca magnéticas entre os íons de terras raras, que são enfraquecidas pelas alterações locais da estrutura atômica induzidas pela compressão da rede cristalina. Já no sistema de perovskitas duplas, foi demonstrado que a compressão da estrutura Sr2FeOsO6, com um arranjo cristalino ordenado dos íons de Fe (3d) e Os (5d), permite o controle contínuo e reversível da coercividade e magnetização de saturação. Este efeito foi explicado em termos do aumento do campo elétrico cristalino em função da pressão, que altera as interações de troca magnéticas Fe-O-Os e transforma o material com magnetização remanente e coercividade praticamente nulas a pressão ambiente em outro com uma coercividade robusta (~0.5 T) e magnetização de saturação expressiva a pressões acima de ~10 GPa. Por fim, a última parte desta tese de doutorado foi dedicada ao uso da seletividade química e orbital da técnica de XANES na investigação do acoplamento spin-órbita nos elementos Pt (Pt0, 5d9) e Hf (Hf0, 5d2) sob altas pressões. Ao contrário do observado para a Pt, o cálculo do branching ratio a partir dos espectros de absorção nas bordas L2,3 do Hf revelaram que o acoplamento spin-órbita aumenta monotonicamente em função da pressão aplicada. Esse comportamento foi relacionado às propriedades supercondutoras e estruturais presentes nesse elemento sob altas pressões / Abstract: The scientific goal of this work has been the investigation of several physical mechanisms derived from the electronic, magnetic and structural properties of ternary rare earth and transition metal systems by means of X-ray absorption spectroscopy and X-ray diffraction techniques in a diamond anvil cell. Among the physical properties studied as a function of lattice compression induced by applied pressure are the magnetism of the 4f and 5d orbitals in tetragonal rare earth rhodium borides RERh4B4 (with RE = Dy e Er), the crystal electric field effects and magnetic exchange interactions in 3d-5d double perovskite systems (A2FeOsO6, with A = Ca e Sr) and the spin-orbit coupling in 5d transition metals. The electronic and magnetic properties of the rare earth 4f and 5d orbitals in the RERh4B4 (RE = Dy e Er) systems were investigated through high pressure XANES and XMCD experiments at Dy and Er L3 edges. For both compounds, the magnetic signals of the quadrupole (2p3/2->4f) and dipole (2p3/2->5d) contributions to the XMCD spectra progressively decrease as a function of pressure. This behavior was explained in terms of the magnetic exchange interactions between the rare earth ions, which are weakened by changes in the local atomic structure induced by compression of the crystal lattice. In the double perovskite system, it has been shown that compression of Sr2FeOsO6 structure with an ordered crystalline arrangement of iron (3d) and osmium (5d) transition metal ions, allows for continuous and reversible control of magnetic coercivity and saturation magnetization. This effect was explained in terms of enhanced crystal electric fields under high pressure, which alter the Fe-O-Os magnetic exchange interactions and transform the material with an otherwise mute response to magnetic fields into one with a strong coercivity (~0.5 T) and substantial saturation magnetization at pressures above ~10 GPa. Finally, the last part of this thesis is dedicated to the use of chemical and orbital selectivity of XANES technique as a tool to investigate the spin-orbit coupling in Pt (Pt0, 5d9) and Hf (Hf0, 5d2) elements under high pressures. Unlike observed for Pt, the calculated branching ratio determined from the integrated intensities of the Hf L2,3 white lines shows that the spin-orbit coupling increases monotonically as a function of applied pressure. This behavior was related to the superconducting and structural properties displayed by this element at high pressures / Doutorado / Física / Doutora em Ciências