Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A theoretical study of the interactions between the 4f electrons in lanthanide ions (Ln3 +) with the chemical environment was made using crystal field theory. The main effects were studied: change in position of the berycentre of the energy levels of the free ion, maximum splitting of the J level and contribution to 5D0-7F0 transition of Eu3+ ion. Use of second-order correction to the wave functions allow a better understanding the relationship between the maximum splitting 7F1 Eu3+ ion and the position of its berycentre. The dependence between the intensity of the 5D0-7F0 transition with its position was also demonstrated using the linear part of the crystal field. This study was done based on symmetry properties of the Hamiltonian of the free ion and crystal field. The predicted position of the berycentre and the maximum splitting of the 7F1 level are in good agreement with the experimental results. The equations for the 5D0-7F0 transition satisfactorily reproduced the experimental data and can be used for the Sm2+ ion. / Um estudo teórico das interações entre os elétrons 4f de íons lantanídeos (Ln3+) íon com o meio químico foi feito usando a teoria de campo cristalino. Os principais efeitos estudados foram: mudança na posição do baricentro dos níveis de energia do íon livre, desdobramento máximo do nível J e contribuição para transição 5D0-7F0 do íon Eu3+. Usar a correção de segunda ordem para as funções de onda permitiu entender melhor como é a relação entre o desdobramento máximo do 7F1 do íon Eu3+ e a posição de seu baricentro. A dependência entre intensidade da transição 5D0-7F0 com a sua posição também foi demonstrada usando a parte linear do campo cristalino. Este estudo foi feito baseado em propriedades de simetria do hamiltoniano do íon livre e do campo cristalino. A previsão da posição do baricentro e do desdobramento do nível 7F1 estão em bom acordo com os resultados experimentais. As equações obtidas para a transição 5D0-7F0 reproduziram satisfatoriamente os resultados experimentais e podem ser usadas para o íon Sm2+.

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No. of bitstreams: 1 victorhugofelipebernardes.pdf: 4330159 bytes, checksum: 8ed0f32ccd734b911991c27470472e98 (MD5) Previous issue date: 2012-08-03 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / Este trabalho descreve a síntese e caracterização de oito complexos envolvendo os ligantes N,O doadores, piridino-3,5-dicarboxilato (3,5-pdc); piridino2,5-dicarboxilato (2,5-pdc); piridino-2,6-dicarboxilato (2,6-pdc) e isonicotinato (iso). Todos os compostos foram caracterizados por espectroscopia de absorção atômica de chama, espectroscopia vibracional na região do infravermelho e Raman, análise elementar de CHN e análise térmica (TG/DTA). As caracterizações indicam que seis desses complexos são heterobimetálicos do tipo 3d-4f, ou seja, apresentam em sua fórmula molecular um metal do bloco d [Co(II) ou Cu(II)] e um metal do bloco f [Eu(III) ou Sm(III)]. As caracterizações sugerem ainda que os complexos EuCo(3,5pdc) e EuCu(3,5-pdc) sejam isoestruturais, assim como os compostos SmCu(2,5pdc), EuCo(2,5-pdc) e EuCu(2,5-pdc). Outros dois complexos intitulados Co(3,5-pdc) e Eu(iso) tiveram suas estruturas determinadas através da difração de raios X por monocristal. A estrutura do complexo Co(3,5-pdc) pertence ao sistema cristalino monoclínico, grupo espacial P21/n, apresentando a fórmula molecular [Co(3,5pdc)(H2O)5]dmso. O sítio de Co(II) apresenta geometria octaédrica distorcida, sendo a esfera de coordenação composta por cinco ligantes aqua e um átomo de nitrogênio do ligante 3,5-pdc. Nesse caso, os grupos carboxilatos do 3,5-pdc não estão envolvidos na coordenação. O composto Eu(iso) com fórmula mínima [Eu(iso)3(H2O)2]n cristalizou-se no sistema monoclínico, pertencendo ao grupo espacial P21/c e mostrou-se como um polímero de coordenação 1D. O íon Eu(III) está coordenado a oito átomos de oxigênio apresentando geometria antiprismática quadrada distorcida. Os ligantes iso adotam dois modos de coordenação: bidentado quelato e em ponte. Os compostos heterobimetálicos juntamente com o complexo Eu(iso), foram estudados por espectroscopia de luminescência. Os espectros de luminescência indicam que a excitação direta no comprimento de onda da transição π→π* do ligante é mais eficiente que a excitação direta no metal, caracterizando a sensibilização do lantanídeo. O diagrama de cromaticidade CIE revela que as emissões apresentam alta pureza, com coordenadas X e Y próximas da borda. / This work describes the synthesis and characterization of eight complexes involving the N,O-donor ligands, pyridine-3,5-dicarboxylate (3,5-pdc); pyridine-2,5dicarboxylate (2,5-pdc); pyridine-2,6-dicarboxylate (2,6-pdc) and isonicotinate (iso). All compounds were characterized by atomic absorption spectroscopy, infrared and Raman vibrational spectroscopies, CHN elemental analysis and thermal analysis (TG/DTA). The characterization techniques indicate that six of these are 3d-4f heterobimetallic complexes, in other words, present in their molecular formulae a dblock metal [Co (II) or Cu (II)] and a f-block metal [Eu (III) or Sm (III)]. The characterization techniques also suggest that complexes EuCo(3,5-pdc) and EuCu(3,5-pdc) are isostructural, as well as compounds SmCu(2,5-pdc), EuCo(2,5pdc) and EuCu(2,5-pdc). Two other complexes entitled Co(3,5-pdc) and Eu(iso) had their structures determined by single-crystal X-ray diffraction analysis. Complex Co(3,5-pdc) structure belongs to the monoclinic crystal system, space group P21/n, with molecular formula [Co(3,5-pdc)(H2O)5]dmso. Co(II) sites adopt a distorted octahedral geometry, with the coordination sphere composed of five aqua ligands and one nitrogen atom from 3,5-pdc ligand. In this case, the 3,5-pdc carboxylate groups are not involved in coordination. Eu(iso) compound, with molecular formula [Eu(iso)3(H2O)2]n crystallized in the monoclinic system, belonging to space group P21/c and appeared as a 1D coordination polymer. The Eu(III) ion is coordinated to eight oxygen atoms displaying distorted square antiprismatic geometry. The iso ligands adopt two coordination modes: bidentate chelate and bridging. The heterobimetallic compounds along with the complex Eu(iso), were studied by luminescence spectroscopy. The luminescence spectra indicate that the direct excitation wavelength of the π → π* transition of the ligands is more efficient than direct excitation into the metal, characterizing lanthanide sensitization. The CIE chromaticity diagram shows that the emissions have high purity, with X and Y coordinates near the edge.

The search for novel technologies like spin-based electronics and suitable materials for respective devices requires a profound understanding of fundamental interactions regarding electron spin and related properties. In the same context, with ongoing device miniaturisation, surface-related phenomena become increasingly important. Here, we study the electronic and magnetic properties of quasi-2D electron states at a metallic surface under the influence of the Rashba effect and exchange coupling to localised 4f moments that order magnetically at low temperatures. Particularly, in the considered systems, both interactions are of similar strengths, a case which is rather unexplored in the literature. Our model system is the (001) surface of intermetallic LnIr2Si2 compounds with ThCr2Si2 structure, where Ln = lanthanide. With this work, we continue our long-term systematic study of the LnT2Si2 compounds with T = Rh, where the Rashba-like spin-orbit coupling is about a hundred times weaker than the exchange interaction. Using ARPES and DFT we explore with GdIr2Si2 and EuIr2Si2 two representatives of the LnIr2Si2 family, which are both characterised by the insensitivity of the 4f shell to the crystal electric field. On the other hand, they have fundamentally different bulk properties. GdIr2Si2 is a robust bulk antiferromagnet with a high ordering temperature of 87 K, whereas EuIr2Si2 is a mixed-valent material with a non-magnetic ground state in the bulk. The mean Eu valency is strongly temperature dependent, changing continuously from a nearly divalent magnetic configuration at room temperature to a nearly trivalent non-magnetic Eu state below 50K. Studying the surface states in both compounds we find that the magnitude of the Rashba-like spin-orbit interaction increases tremendously in comparison to the isoelectronic Rh compounds. This is reflected in a huge splitting of the surface state bands and emphasizes the importance of atomic spin-orbit coupling in high Z elements for the strength of the Rashba effect. Employing DFT, which reproduces the measured band structure very accurately, we find the same exotic triple winding of the electron spin along the isoenergy contours of the surface state bands as reported in terms of a cubic Rashba effect for the Rh compounds. This proves the generic nature of the surface states and their universal properties in the considered LnT2Si2 compounds. With the ordering of the 4f moments at low temperatures, spin structure and surface band dispersion undergo significant changes induced by the exchange interaction. Pronounced asymmetries emerge in the band dispersion, which allow for the determination of the magnetisation axis. We demonstrate that this is even possible if spectral structures originating from different magnetic domains overlap in the spectra. Remarkably, we find respective asymmetries in EuIr2Si2, too, despite the almost trivalent, and thus non-magnetic Eu state at low temperatures. With complementary experimental techniques like x-ray absorption, x-ray linear and circular dichroism as well as by taking photoelectron diffraction into account, we demonstrate that in the surface Si–Ir–Si–Eu four-layer block Eu is nearly divalent and magnetically active. The associated Eu moments order ferromagnetically below 49K. In the case of Eu termination, we find that the 4f moments of the divalent Eu ions at the surface order ferromagnetically below 10K, too, and unveil thus another occurrence of 2D surface-related magnetism in the same non-magnetic bulk compound. Simultaneously, the mixed-valent properties of EuIr2Si2 and the strong temperature dependence of the mean Eu valency are clearly reflected in the electronic structure of the bulk in a smooth expansion of the Doughnut Fermi surface sheet with increasing temperature, which is interpreted as a band-filling effect. Our results show the high tunability of the electron spin by combining spin-orbit coupling and structural inversion asymmetry with the exchange interaction, which is at the heart of spintronics applications. The disclosure of controllable 2D magnetism at the surface of a non-magnetic bulk compound, which is enabled by an instability in the 4f shell, nominates valence fluctuating 4f compounds, especially with Eu and Sm, to be promising candidates for fundamental studies and applications. Our study moreover demonstrates the richness and versatility of 4f physics that may differ significantly at the surface and in the bulk.:1. Introduction 2. Preliminary Studies 2.1. Short introduction to lanthanides and 4f physics 2.2. LnT2Si2 compounds 3. Foundations 3.1. Band structure 3.2. Bulk states, surface states and surface resonances 3.3. The principles of photoelectron spectroscopy 3.4. Angle-resolved photoelectron spectroscopy 3.5. Photoabsorption and resonant photoelectron spectroscopy 3.6. X-ray absorption spectroscopy 3.6.1. X-ray magnetic circular dichroism 3.6.2. X-ray magnetic linear dichroism 3.7. Photoelectron diffraction 3.8. Synchrotron and synchrotron radiation 3.9. Density functional theory 4. Methods 4.1. Experimental details 4.2. DFT calculations 5. GdIr2Si2 5.1. Introduction 5.2. Results and discussion 5.2.1. Paramagnetic phase 5.2.2. Magnetically ordered phase 5.3. Summary 6. EuIr2Si2 6.1. Introduction 6.2. Results and discussion 6.2.1. Photoemission from the Eu 4f shell 6.2.2. ARPES on the Si-terminated surface 6.2.3. X-ray magnetic linear and circular dichroism 6.2.4. Eu termination 6.2.5. Determination of the mean Eu valency in the subsurface layers 6.2.6. Bulk properties 6.3. Summary 7. Conclusion / Die Suche nach neuartigen Technologien wie spinbasierte Elektronik sowie nach geeigneten Materialien für entsprechende Bauteile erfordert ein tiefgreifendes Verständnis der Wechselwirkungen des Elektronenspins und damit verbundener Materialeigenschaften. Mit der zunehmenden Miniaturisierung von Bauteilen gewinnen in diesem Zusammenhang auch Oberflächenphänomene zunehmend an Bedeutung. In dieser Arbeit untersuchen wir die elektronischen und magnetischen Eigenschaften quasizweidimensionaler elektronischer Zustände an metallischen Oberflächen unter dem Einfluss des Rashba-Effekts und der Austauschwechselwirkung mit lokalisierten 4f Momenten, die bei tiefen Temperaturen magnetisch ordnen. Dabei liegt die Besonderheit der untersuchten Systeme darin, dass beide Wechselwirkungen von vergleichbarer Stärke sind. Dieser Fall ist in der Fachliteratur bislang unterrepräsentiert. Unser Modellsystem ist die (001)-Oberfläche intermetallischer LnIr2Si2 Verbindungen mit ThCr2Si2 Struktur, wobei Ln ein Lanthanoidenelement darstellt. Dabei führen wir die langjährige und systematische Untersuchung von LnT2Si2 Verbindungen mit T = Rh fort, in denen die Rashba-artige Spin-Bahn-Kopplung ungefähr 100-mal schwächer als die Austauschwechselwirkung ist. Mit Hilfe von winkelaufgelöster Photoelektronenspektroskopie (ARPES) und Dichtefunktionaltheorie (DFT) erkunden wir mit GdIr2Si2 und EuIr2Si2 zwei Vertreter der LnT2Si2 Familie, die beide durch die Insensibilität der 4f Schale gegenüber dem Kristallfeld ausgezeichnet sind. Zugleich haben sie grundsätzlich verschiedene Volumeneigenschaften. GdIr2Si2 ist ein robuster Volumenantiferromagnet mit einer hohen Ordnungstemperatur von 87K, wohingegen EuIr2Si2 eine gemischtvalente Verbindung mit einem nicht-magnetischen Volumengrundzustand ist. Die mittlere Eu Valenz ist stark temperaturabhängig, sie ändert sich kontinuierlich von einer nahezu zweiwertigen Konfiguration bei Raumtemperatur zu einem beinahe dreiwertigen, nicht-magnetischen Eu Zustand unterhalb von _ 50K. Die Untersuchung der Oberflächenzustände in beiden Verbindungen zeigt, dass die Stärke der Rashba-artigen Spin-Bahn-Kopplung gegenüber den isoelektronischen Rh Verbindungen erheblich zunimmt. Dies spiegelt sich in einer riesigen Aufspaltung der Oberflächenbänder wider und unterstreicht die Bedeutung der atomaren Spin-Bahn-Kopplung in Elementen mit großer Kernzahl Z für die Stärke des Rashba-Effekts. Unsere DFT Rechnungen reproduzieren die gemessene Bandstruktur mit hoher Genauigkeit und offenbaren dieselbe Dreifachwindung des Spins entlang der Konturen konstanter Energie, die schon als kubischer Rashba-Effekt in den Rh Verbindungen beobachtet wurde. Hierin zeigt sich das allgemeingültige Wesen der Oberflächenzustände und deren universelle Eigenschaften in den betrachteten LnT2Si2 Verbindungen. Das Ordnen der 4f Momente bei niedrigen Temperaturen führt zu starken Veränderungen in der Spinstruktur und der Dispersion der Oberflächenbänder durch die einsetzende Austauschwechselwirkung. In der Bandstruktur bilden sich starke Asymmetrien, aus denen die Magnetisierungsachse bestimmt werden kann. Wir zeigen, dass dies sogar dann noch möglich ist, wenn sich spektrale Strukturen überlagern, die von unterschiedlichen magnetischen Domänen stammen. Besonders bemerkenswert ist, dass entsprechende Asymmetrien auch in EuIr2Si2 auftreten, trotz des nahezu dreiwertigen und damit nicht-magnetischen Eu bei tiefen Temperaturen. Mit komplementären experimentellen Methoden wie Röntgenabsorption, linearem und zirkularem Röntgendichroismus als auch durch die Berücksichtigung von Beugungseffekten in der Photoelektronenspektroskopie zeigen wir, dass Eu im Si–Ir–Si–Eu Oberflächenblock beinahe zweiwertig und magnetisch aktiv ist. Die zugehörigen Eu Momente ordnen unterhalb von 49K ferromagnetisch. Im Fall der Eu-Terminierung stellen wir fest, dass auch die 4f Momente der zweiwertigen Eu-Ionen an der Oberfläche unterhalb von 10K ferromagnetisch geordnet sind, und enthüllen damit ein weiteres Vorkommen zweidimensionalen, oberflächenbezogenen Magnetismus in derselben, nichtmagnetischen Volumenverbindung. Gleichzeitig spiegeln sich die gemischtvalenten Eigenschaften von EuIr2Si2 deutlich in der elektronischen Volumenbandstruktur in einer kontinuierlichen Ausdehnung der Doughnut-Fermifläche mit steigender Temperatur wider. Dies interpretieren wir als Bandfüllungseffekt. Unsere Ergebnisse zeigen die hohe Einstellbarkeit des Elektronenspins durch die Kombination von Spin-Bahn-Kopplung und struktureller Inversionsasymmetrie mit der Austauschwechselwirkung, was die Grundlage für Anwendungen in der spinbasierten Elektronik bildet. Die Enthüllung von kontrollierbarem, zweidimensionalem Magnetismus an der Oberfläche einer Verbindung mit instabiler 4f Schale, die im Volumen nicht-magnetisch ist, nominiert gemischtvalente 4f Verbindungen, insbesondere mit Eu und Sm, als vielversprechende Kandidaten für Grundlagenforschung und Anwendungen. Unsere Studie zeigt zudem den Reichtum und die Vielseitigkeit von 4f Systemen, deren Eigenschaften sich an der Oberfläche deutlich vom Volumen unterscheiden können.:1. Introduction 2. Preliminary Studies 2.1. Short introduction to lanthanides and 4f physics 2.2. LnT2Si2 compounds 3. Foundations 3.1. Band structure 3.2. Bulk states, surface states and surface resonances 3.3. The principles of photoelectron spectroscopy 3.4. Angle-resolved photoelectron spectroscopy 3.5. Photoabsorption and resonant photoelectron spectroscopy 3.6. X-ray absorption spectroscopy 3.6.1. X-ray magnetic circular dichroism 3.6.2. X-ray magnetic linear dichroism 3.7. Photoelectron diffraction 3.8. Synchrotron and synchrotron radiation 3.9. Density functional theory 4. Methods 4.1. Experimental details 4.2. DFT calculations 5. GdIr2Si2 5.1. Introduction 5.2. Results and discussion 5.2.1. Paramagnetic phase 5.2.2. Magnetically ordered phase 5.3. Summary 6. EuIr2Si2 6.1. Introduction 6.2. Results and discussion 6.2.1. Photoemission from the Eu 4f shell 6.2.2. ARPES on the Si-terminated surface 6.2.3. X-ray magnetic linear and circular dichroism 6.2.4. Eu termination 6.2.5. Determination of the mean Eu valency in the subsurface layers 6.2.6. Bulk properties 6.3. Summary 7. Conclusion

Выполнено систематическое исследование магнитных свойств аморфных плёнок (РЗМ)xCo100-x, содержащих редкоземельные металлы РЗМ различного типа: La не имеет магнитного момента; Gd обладает сферической электронной оболочкой; Tb характеризуется анизотропией электронной структуры. На основе анализа спонтанной намагниченности плёнок определены концентрационные зависимости средних атомных магнитных моментов кобальта (mCo), гадолиния (mGd) и тербия (mTb). Показано, что в интервале 0 < x < 50 % mCo уменьшается от 1,7 µB до нуля, mGd не меняется и практически совпадает с магнитным моментом свободного атома (7 µB), а mTb монотонно снижается, причем скорость уменьшения зависит от способа получения образцов. Найденные закономерности связываются с концентрационным изменением электронной структуры Со и спецификой магнитной структуры плёнок, которая имеет ферромагнитный, ферримагнитный или сперимагнитный характер для образцов, содержащих La, Gd или Tb соответственно. Установлено, что в пленках систем Gd-Co и Tb-Co может присутствовать одноосная магнитная анизотропия, сильно различающаяся по своей величине. Механизм её формирования может быть связан с упорядочением пар атомов в GdxCo100-x и магнитострикционной деформацией или проявлением локальной анизотропии атомами тербия в TbxCo100-x. / A systematic study of magnetic properties of (RE)xCo100-x amorphous films, containing rare earth metals of various types, was conducted: La has no magnetic moment; Gd has a spherical electron shell; Tb is characterized by anisotropy of the electron structure. Concentration dependences of average atomic magnetic moments of cobalt (mCo), gadolinium (mGd), and terbium (mTb) were determined based on the films spontaneous magnetization analysis. It was shown that mCo decreases in the range of 0 < x < 50 % from 1.7 μB to zero, mGd does not change and it is almost identical to the magnetic moment of a free atom (7 μB), and mTb decreases monotonically, and the reduction rate depends on the method of samples preparation. The observed behavior is associated with the change in the electron shell of Co and specificity of the films magnetic structure, which is ferromagnetic, ferrimagnetic or sperimagnetic for the samples, containing La, Gd, and Tb, respectively. It was found that Gd-Co and Tb-Co systems films can demonstrate uniaxial anisotropy of considerably different magnitude. The mechanism of its formation may be associated with the atoms pairs ordering in GdxCo100-x and magnetostrictive deformation or manifestation of the local anisotropy of terbium atoms in TbxCo100-x.

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