Due to recent progress in theory and the growing number of physical realizations, low-dimensional quantum magnets continue to receive a considerable amount of attention. They serve as model systems for investigating numerous physical phenomena in spin systems with cooperative ground states, including the field-induced evolution of the ground-state properties and the corresponding rearrangement of their low-energy excitation spectra. This work is devoted to systematic studies of recently synthesized low-dimensional quantum spin systems by means of multi-frequency high-field electron spin resonance (ESR) investigations. In the spin- 1/2 chain compound (C6H9N2)CuCl3 [known as (6MAP)CuCl3] the striking incompatibility with a simple uniform S = 1/2 Heisenberg chain model employed previously is revealed. The observed ESR mode is explained in terms of a recently developed theory, revealing the important role of the alternation and next-nearest-neighbor interactions in this compound. The excitations spectrum in copper pyrimidine dinitrate [PM·Cu(NO3)2(H2O)2]n, an S = 1/2 antiferromagnetic chain material with alternating g-tensor and Dzyaloshinskii-Moriya interaction, is probed in magnetic fields up to 63 T. To study the high field behavior of the field-induced energy gap in this material, a multi-frequency pulsed-field ESR spectrometer is built. Pronounced changes in the frequency-field dependence of the magnetic excitations are observed in the vicinity of the saturation field, B ∼ Bs = 48.5 T. ESR results clearly indicate a transition from the soliton-breather to a spin-polarized state with magnons as elementary excitations. Experimental data are compared with results of density matrix renormalization group calculations; excellent agreement is found. ESR studies of the spin-ladder material (C5H12N)2CuBr4 (known as BPCB) completes the determination of the full spin Hamiltonian of this compound. ESR results provide a direct evidence for a pronounced anisotropy in this compound, that is in contrast to fully isotropic spin-ladder model employed previously for BPCB. Our observations can be of particular importance for describing the rich temperature-field phase diagram of this material. The frequency-field diagram of magnetic excitations in the quasi-two dimensional S = 1/2 compound [Cu(C4H4N2)2(HF2)]PF6 in the AFM-ordered state is studied. The AFM gap is observed directly. Using high-field magnetization and ESR results, parameters of the effective spin-Hamiltonian (exchange interaction, anisotropy and g-factor) are obtained and compared with those estimated from thermodynamic properties of this compound.

Spatial confinement of electrons and their interactions as well as confinement of the spin dimensionality often yield drastic changes of the electronic and magnetic properties of solids. Novel quantum transport and optical phenomena, involving electronic spin degrees of freedom in semiconductor heterostructures, as well as a rich variety of exotic quantum ground states and magnetic excitations in complex transition metal oxides that arise upon such confinements, belong therefore to topical problems of contemporary condensed matter physics. In this work electron spin systems in reduced dimensions are studied with Electron Spin Resonance (ESR) spectroscopy, a method which can provide important information on the energy spectrum of the spin states, spin dynamics, and magnetic correlations. The studied systems include quasi onedimensional spin chain materials based on transition metals Cu and Ni. Another class of materials are semiconductor heterostructures made of Si and Ge. Part I deals with the theoretical background of ESR and the description of the experimental ESR setups used which have been optimized for the purposes of the present work. In particular, the development and implementation of axial and transverse cylindrical resonant cavities for high-field highfrequency ESR experiments is discussed. The high quality factors of these cavities allow for sensitive measurements on μm-sized samples. They are used for the investigations on the spin-chain materials. The implementation and characterization of a setup for electrical detected magnetic resonance is presented. In Part II ESR studies and complementary results of other experimental techniques on two spin chain materials are presented. The Cu-based material Linarite is investigated in the paramagnetic regime above T > 2.8 K. This natural crystal constitutes a highly frustrated spin 1/2 Heisenberg chain with ferromagnetic nearest-neighbor and antiferromagnetic next-nearestneighbor interactions. The ESR data reveals that the significant magnetic anisotropy is due to anisotropy of the g-factor. Quantitative analysis of the critical broadening of the linewidth suggest appreciable interchain and interlayer spin correlations well above the ordering temperature. The Ni-based system is an organic-anorganic hybrid material where the Ni2+ ions possessing the integer spin S = 1 are magnetically coupled along one spatial direction. Indeed, the ESR study reveals an isotropic spin-1 Heisenberg chain in this system which unlike the Cu half integer spin-1/2 chain is expected to possess a qualitatively different non-magnetic singlet ground state separated from an excited magnetic state by a so-called Haldane gap. Surprisingly, in contrast to the expected Haldane behavior a competition between a magnetically ordered ground state and a potentially gapped state is revealed. In Part III investigations on SiGe/Si quantum dot structures are presented. The ESR investigations reveal narrowlines close to the free electron g-factor associated with electrons on the quantum dots. Their dephasing and relaxation times are determined. Manipulations with sub-bandgap light allow to change the relative population between the observed states. On the basis of extensive characterizations, strain, electronic structure and confined states on the Si-based structures are modeled with the program nextnano3. A qualitative model, explaining the energy spectrum of the spin states is proposed.

Thesis (Ph. D.)--University of Virginia, 2008. / Title from title page. Includes bibliographical references. Also available online through Digital Dissertations.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-22T12:40:27Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-22T12:40:27Z (GMT). No. of bitstreams: 0 / Foram estudados as propriedades de absorção ótica, de termoluminescência e de ressonância paramagnética eletrônica do mineral natural de silicato de nome MONTICELITA do grupo Olivina, para caracterização desse mineral, cuja formula química é CaMgSiO4. A absorção ótica mostrou que há três bandas de absorção em 450 nm, 660 nm e 1050 nm. As duas primeiras bandas, a primeira no azul e a segunda no amarelo-vermelho são responsáveis pela cor verde da Monticelita. Essas duas bandas são consequência do elemento cromo contido no mineral absorver fótons do feixe universal no visível de frequências centradas em 450 nm e 660 nm. A banda em 1050 nm é devido ao Fe2+. As curvas de emissão de uma amostra de Monticelita irradiada com raios gama de doses entre 10 e 1000 Gy apresenta três picos em 150 °C , 270 °C e 370 °C . Pelo método da deconvolução e de várias taxas de aquecimento foram obtidos energia E1=1,35 eV e fator de frequência s1=4,98x1011 s-1 para o pico 270 °C e E2=1,70 eV e s2=1,88x1011 s-1 para pico 370 °C . A irradiação com raios gama de doses entre 5 kGy e 50 kGy produziram pico TL de 380 °C com intensidade TL em função da dose linear e crescente. Este resultado e importante para dosimetria da radiação de altas doses. O espectro EPR de uma amostra natural, mostrou um resultado não esperado e interessante. Além dos sinais típicos de interação hiperfina do Mn2+, um sinal avantajado de g =6,34 indica que o ferro formou moléculas de hematita, Fe2O3. Esse sinal desaparece com aquecimento acima de 800 °C de recozimento, dando origem dipolos magnéticos de Fe3+, que dá origem a um sinal típico em g =2. Esta descrição mostra bem a caracterização do mineral Monticelita. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Brazil nuts (Bertholletia excelsa, H.B.K.) are seeds of high nutritional value collected from South American rainforests and its productive chain is one of the most important non-timber economic activities in Brazilian amazon. The main objectives of this research were: 1) characterize the occurrence of chemical changes in Brazil nut kernels (BNK), cold-pressed Brazil nut oil (BNO) and Brazil nut flour obtained by water extraction (BNF); and 2) investigate strategies of control and monitoring these changes during storage. For this, consolidated techniques, such as spectrophotometry and chromatography, and a relatively new analytical technique, the electron spin resonance (ESR) spectroscopy, were employed. As major results, it was found that different combinations of storage temperatures and atmosphere packages have differently affected the tendency of radical formation and off-flavor volatile aroma compounds generation in BNK, and that the combination of refrigeration with vacuum packing was able to keep BNK at their best. It was demonstrated that a spin-trapping ESR spectroscopy method would be suitable to monitor oxidative changes in BNO with known history stored either in clear or in brown glass bottles under retail conditions. For BNF, it was demonstrated that minor variations on water activity (aw) might significantly affect the rates of both lipid oxidation and nonenzymatic browning reactions during storage. There was indication that for BNF with initial aw of 0.196, but not for BNF with initial aw of 0.101, under the studied conditions, secondary products from lipid oxidation might be substrates for nonenzymatic browning products formation. As a conclusion, these results may help to better understand chemical deteriorative processes in BNK and its co-products, according to the storage conditions, and that the use of less sample-demanding, fast and solvent-free analytical method to monitor these changes in BNO is feasible. / A castanha do Brasil (Bertholletia excelsa, H.B.K.) é uma semente de boa qualidade nutricional coletada em florestas tropicais da América do Sul, cuja cadeia produtiva é uma das mais importantes atividades econômicas não madeireiras da Amazônia brasileira. Os principais objetivos desta pesquisa foram: 1) caracterizar a ocorrência de alterações químicas em castanhas do Brasil (CB), óleo de castanha do Brasil obtido por prensagem a frio (OCB) e farinha de castanha do Brasil obtida por extração aquosa (FCB); e 2) investigar estratégias para controlar e monitorar essas alterações ao longo do armazenamento. Para isso, técnicas consolidadas como a espectrofotometria e a cromatografia, e uma técnica relativamente recente, a espectroscopia de ressonância de spin eletrônico (RSE), foram empregadas. Dentre os principais resultados obtidos, foi possível constatar o efeito de diferentes combinações de temperaturas e atmosferas de embalagem sobre a tendência de formação de radicais e sobre a geração de compostos voláteis de aroma relacionados a odor indesejável em CB, e que a temperatura de refrigeração combinada com a embalagem a vácuo foi a mais eficiente na preservação da qualidade da CB. Demonstrou-se que o uso de um método de aprisionamento de spins de RSE pode ser eficiente para monitorar alterações químicas em OCB com histórico conhecido embalado em frascos de vidro transparente ou marrons sob condições de armazenamento comercial. Para FCB, foi demonstrado que pequenas variações na atividade de água (aw) podem afetar significativamente as taxas de oxidação lipídica e de reações de escurecimento não enzimático durante armazenamento. Obteve-se indicação de que para FCB com aw inicial de 0,196, mas não para FCB com aw inicial de 0,101, produtos secundários da oxidação lipídica podem ser substratos para a formação de produtos do escurecimento não enzimático. Como conclusão geral, os resultados obtidos podem ajudar a explicar melhor os processos de deterioração química em CB e seus coprodutos, conforme as condições de armazenamento, e que o uso de um método que requer menor quantidade de amostras, é rápido e não usa solventes é viável para o monitoramento da qualidade de OCB.

For every phenomenon found in inorganic materials, organic counterparts have been found in the last 50 years. The discovery of metallic conductivity in the inorganic conjugated polymer (SN)x was a forerunner to the discovery of metallic conductivity in Polyacetylene [1]. It was soon followed by the development of Polypyrrole and Polythiophene, and by the rediscovery of Polyaniline as a conducting polymer [2]. In polymers like Polyacetylene and Polythiophene, doping is by a redox reaction where the incorporation of electron withdrawing groups creates charge carriers in the polymer backbone. In contrast to these polymers, the main doping mechanism in Polyaniline is protonation, that is the attachment of a proton (donated by an acid) to specific sites (imine and amine groups) in the polymer. The protonated groups are also the sites where water and oxygen interact with the charge carriers on the polymer chain. A wide variety of quasi-particle states (excitons, bipolarons, separated polarons and polaron lattice forms) exist in Polyaniline, in its different states of oxidation and protonation. All of them have different transport and optical signatures. Out of these, only the polaron lattice gives rise to a half-filled conduction band, and therefore a metallic state [3]. This fascinating interplay of protonation and metallic features in Polyaniline, combined with its easy processibility, has made Polyaniline an attractive conducting polymer. Therefore the main focus of this thesis is on the role of the dopant on the electronic and optical properties of doped Polyaniline. The first chapter describes the main features of Polyaniline and its doping by protonation. The second chapter describes the experimental and simulation methods used in this thesis. Steady improvements in processing have led to reduced disorder in the samples, and have given rise to stronger metallic features like metallic (Drude-like) reflectivity in the infrared frequencies, and a positive temperature coefficient of the logarithmic derivative of the conductivity. High molecular weight Polyaniline doped with sulfonic acid dopants by surfactant-counterion processing, like Polyaniline doped with AMPSA (2-acrylamido-2-methyl-1-propanesulfonic acid) [4] and cast from dichloroacetic acid (DCA), shows all the metallic features indicative of an intrinsic metallic state [5]. In this thesis, the third chapter describes the spin-charge dynamics of Polyaniline doped with AMPSA (PANIAMPSA) through X-band Electron Spin Resonance studies [6]. Electron Spin Resonance (ESR) is an important technique to probe the spin-charge dynamics of conducting polymers [7, 8]. The X-band ESR spectra of PANI doped with AMPSA showed the presence of two lines (one broad and one narrow) at all temperatures and doping levels, indicative of two types of spin carriers. Three interesting features were observed in our study: a large linewidth ( ~100 Gauss), a maximum of ESR linewidth at ~ 25 K, and a surprising independence of linewidth on water/O2 . The temperature dependence of both linewidths suggests that the broad line is due to the delocalised charge carriers in well-ordered regions, and that the narrow line is due to localised spins in the disordered regions in the sample. Although the XRD spectra showed minimal crystallinity, the ESR and SQUID susceptibility had a strong Pauli contribution, indicative of an intrinsic metallic state. A similarity of the temperature dependence of linewidths of PANI-AMPSA with MWNT-s and HOPG graphite suggested that some quasi-2-D (Q2D) ordering is present in PANI-AMPSA. From Semi-empirical molecular modelling studies, a plausible hydrogen bonding pattern is suggested that can give rise to the Q2D graphene-like arrangement of the PANI polymer chains. This ordering is due to hydrogen bonding between the acrylamido group of the dopant and the amine fragment of the Polyaniline backbone. Hydrogen bonds are not just structural linkers between adjacent chains; they can have subtle effects on electronic states of the polymer backbone due to charge transfer/withdrawal by the hydrogen bond from the delocalised β-electron system of the backbone. The same Q2D model is used to explain the water/oxygen independence of linewidth in PANI-AMPSA. The temperature dependence of linewidth of both lines has been explained in terms of the QTDG (Quasi Two Dimensional Graphite) model, where a strong exchange interaction is presumed to arise between the 2D delocalised charge carriers and the localised spins, leading to a low-temperature peak in the the linewidth. Water is known to significantly enhance the conductive properties of doped Polyaniline [9]. A detailed DFT (Density Functional Theory) modelling study of the influence of water in doped Polyanilines is presented, which clearly indicated that water enhances the charge transfer between the counterion and the polymer backbone. The torsion angles between the adjacent phenyl rings of the emeraldine base decrease when the imine nitrogens are protonated by inorganic acids like HCl and HBr, and hydration of the acid counterions further decrease the torsion angles. In contrast, the torsion angles of the AMPSA protonated Polyaniline are already low (comparable to the hydrated cases), and the charge transferred by AMPSA is also enhanced. Visualisation of the molecular structure of the PANI-AMPSA complex suggested that water molecules may play a minimal role in the electronic properties of AMPSA doped Polyaniline. We suggest the Q2D ordering as the reason for the temperature dependence of the linewidth, the lack of oxygen and water dependence of the linewidth, as well as the enhanced metallic properties in PANI-AMPSA, as compared to other doped Polyanilines. The electronic states of Polyaniline are modified by both redox processes and protonation. This gives rise to a wide variety of optical states, which can be easily accessed by both applied potential and pH [10]. Therefore Polyaniline displays strong electrochromism across the visible, near-IR (NIR), IR and even microwave spectral regions. This feature has wide applications in electrochromic devices. However, a fundamental understanding of the phenomena behind this electrochromism, the charge carrier(s) responsible, and the relation of nanoscopic morphology and electrochemical properties to the electrochromism, is still not clear. In the fourth chapter, we have analysed extensive data from electrochromic devices [11]. Clear assignments are that certain population states contribute predominantly to certain spectral regions (e.g. bipolaron states to the IR, the valence band to the visible and other mid-gap states to the microwave). Among more specific findings, a prominent 7µm (0.16 eV) peak in MIR devices is ascribed to bipolarons, while a low-energy transition at 0.054 eV is ascribed to inter/intra-chain transitions. Each of these transitions is tracked with respect to changes in applied potential, as well as correlated with device morphology and construction. Our analysis of UV-Vis-MIR-FIR-microwave results along with detailed SEM data clearly relates performance in different wavelength regions to morphology. Preliminary kinetics analysis show that the diffusion rates in these devices could be improved further. These findings point to the potential design of very broad-band electrochromic systems encompassing the visible through microwave regions. Polyaniline in its insulating states can be considered as a series of linked oligoanilines. These oligoaniline states can either be considered as a model for describing the properties of the polymer, or can be interesting systems themselves in the light of single-molecular electronic devices [12]. Both applied potential and pH can change the electronic states of these systems. The ability of pH to modify the oxidation states in these systems (and induce electronic transport), and the influence of water on these properties can be a model for biological systems too. While a wealth of information on oligoanilines has been generated from experiments, computational modelling of these systems is less reported. Among many computational methods that have been developed for calculation of optical absorption spectra of molecules, Time Dependent Density Functional Theory (TDDFT) is the method with the widest use. TDDFT obtains the excitation energies of a molecule from the linear response of the electronic density to a external perturbing field [13]. Solvent effects, which are known to affect the excitation energies, are included through the SCRF/PCM (Self-consistent Reaction Field/ Polarizable Continuum Model). PCM is a method that treats the solvent molecules as a continuum, and self-consistently evaluates their electronic distribution around the solute. In the fifth chapter, a systematic study of the optical properties of neutral oligoaniline, in three oxidation states, is performed by varying the chain length and linearity of the backbone. The intrinsic accuracy in the excitation energies obtainable by the combined TDDFT/PCM formalism has enabled us to suggest effective oligomer lengths for the optical transitions in Polyaniline; these are 4 rings for emeraldine base, 4–8 rings for leucoemeraldine base and 4 rings for pernigraniline. The sensitivity of the 2.0 eV exciton peak in emeraldine base to the chemical environment is also apparent from this work. The Valence Density of States (VDOS) and vibrational frequencies, that have been obtained in course of these simulations, have been quantitatively analysed and are a useful addition to understanding the optical properties of neutral Polyanilines. A summary of the results of the dopant and water dependence on the electronic and structural properties of protonated oligoanilines was presented in the third chapter; the appendix describes the methodology in detail. It is worthwhile to emphasize that doped Polyaniline is a system where protonation, hydration and extended β-conjugation all occur together synergistically, and a good overall description of this system is necessary. Modelling the doped state of Polyaniline is a bit more difficult, due to spin polarisation. Ideally, conducting Polyaniline should be modelled in the solid state, with neighbouring chains, counterions and water molecules. Water is known to reversibly increase the macroscopic conductivity and ESR linewidth of doped Polyaniline. In the sixth chapter of this thesis, optical spectra of the bipolaron, separated polaron, and the polaron lattice forms of doped Polyaniline, explicitly including the counterions (Cl, Br, AMPSA) are obtained by the TDDFT method. All the polaronic lattice forms show a dominant absorption at 1.0–1.2 eV, with no absorptions in the range 1.4–2.0 eV. The inclusion of water molecules to solvate the counterions is shown to only weakly modify the optical properties in the polaron lattice form. In the case of polarons on a twisted chain, the 1.0 eV peak is shifted to 1.5 eV. For bipolarons, there is an absorption at 1.3–1.5 eV, along with another peak at 1.8 eV. Comparing with experimental spectra we suggest that the 1.5, 2.8 eV set belongs to a polaron lattice form wherein the chains are twisted. However, individually the 1.5 eV peak may equally come from bipolarons or separated polarons. The peak at 1.8 eV may either be ascribed to a bipolaron form (in which case there should be a 1.5 eV peak too), or to an isolated polaron. The isolated polaron may also show a peak at 2 eV and 3.5 eV that is clearly from a residual emeraldine base electronic state. The steady evolution of the (a) 2 eV exciton peak in emeraldine base to a (b) 1.6– 1.8 eV peak (isolated polarons) to a (c) 1.5 eV peak in the bipolaron form to (d) 1.3 eV peak in the separated polaron form to (e) a 1.0–1.2 eV peak in the fully doped metallic polaron lattice form is clear. This steady evolution observed from TDDFT simulations may help in clarifying the experimental assignments, especially in electrochemical studies on Polyaniline. Simulations including the water molecules were performed to study the experimentally observed dramatic changes on hydration in Polyaniline. However hydration of ions is a dynamic process and static geometries may not provide a fully realistic description. Combined ab initio Molecular Dynamics (AIMD) and TDDFT calculations may be necessary to realistically model the transport properties of doped Polyaniline. This chapter tries to lay a foundation for such work. The main results obtained in this thesis are summarized in the conclusion. To conclude, this thesis is on the electronic and optical properties of Polyaniline. An ESR study on AMPSA doped Polyaniline indicated a unique 2D nanoscopic morphology, and this structure was validated by molecular modelling. The detailed analyses on electrochromic devices led us to perform TDDFT simulations of neutral and doped Polyanilines. These simulations have resulted in clear UV-VIS-IR assignments in all forms of Polyaniline.

Due to recent progress in theory and the growing number of physical realizations, low-dimensional quantum magnets continue to receive a considerable amount of attention. They serve as model systems for investigating numerous physical phenomena in spin systems with cooperative ground states, including the field-induced evolution of the ground-state properties and the corresponding rearrangement of their low-energy excitation spectra. This work is devoted to systematic studies of recently synthesized low-dimensional quantum spin systems by means of multi-frequency high-field electron spin resonance (ESR) investigations. In the spin- 1/2 chain compound (C6H9N2)CuCl3 [known as (6MAP)CuCl3] the striking incompatibility with a simple uniform S = 1/2 Heisenberg chain model employed previously is revealed. The observed ESR mode is explained in terms of a recently developed theory, revealing the important role of the alternation and next-nearest-neighbor interactions in this compound. The excitations spectrum in copper pyrimidine dinitrate [PM·Cu(NO3)2(H2O)2]n, an S = 1/2 antiferromagnetic chain material with alternating g-tensor and Dzyaloshinskii-Moriya interaction, is probed in magnetic fields up to 63 T. To study the high field behavior of the field-induced energy gap in this material, a multi-frequency pulsed-field ESR spectrometer is built. Pronounced changes in the frequency-field dependence of the magnetic excitations are observed in the vicinity of the saturation field, B ∼ Bs = 48.5 T. ESR results clearly indicate a transition from the soliton-breather to a spin-polarized state with magnons as elementary excitations. Experimental data are compared with results of density matrix renormalization group calculations; excellent agreement is found. ESR studies of the spin-ladder material (C5H12N)2CuBr4 (known as BPCB) completes the determination of the full spin Hamiltonian of this compound. ESR results provide a direct evidence for a pronounced anisotropy in this compound, that is in contrast to fully isotropic spin-ladder model employed previously for BPCB. Our observations can be of particular importance for describing the rich temperature-field phase diagram of this material. The frequency-field diagram of magnetic excitations in the quasi-two dimensional S = 1/2 compound [Cu(C4H4N2)2(HF2)]PF6 in the AFM-ordered state is studied. The AFM gap is observed directly. Using high-field magnetization and ESR results, parameters of the effective spin-Hamiltonian (exchange interaction, anisotropy and g-factor) are obtained and compared with those estimated from thermodynamic properties of this compound.

Spatial confinement of electrons and their interactions as well as confinement of the spin dimensionality often yield drastic changes of the electronic and magnetic properties of solids. Novel quantum transport and optical phenomena, involving electronic spin degrees of freedom in semiconductor heterostructures, as well as a rich variety of exotic quantum ground states and magnetic excitations in complex transition metal oxides that arise upon such confinements, belong therefore to topical problems of contemporary condensed matter physics. In this work electron spin systems in reduced dimensions are studied with Electron Spin Resonance (ESR) spectroscopy, a method which can provide important information on the energy spectrum of the spin states, spin dynamics, and magnetic correlations. The studied systems include quasi onedimensional spin chain materials based on transition metals Cu and Ni. Another class of materials are semiconductor heterostructures made of Si and Ge. Part I deals with the theoretical background of ESR and the description of the experimental ESR setups used which have been optimized for the purposes of the present work. In particular, the development and implementation of axial and transverse cylindrical resonant cavities for high-field highfrequency ESR experiments is discussed. The high quality factors of these cavities allow for sensitive measurements on μm-sized samples. They are used for the investigations on the spin-chain materials. The implementation and characterization of a setup for electrical detected magnetic resonance is presented. In Part II ESR studies and complementary results of other experimental techniques on two spin chain materials are presented. The Cu-based material Linarite is investigated in the paramagnetic regime above T > 2.8 K. This natural crystal constitutes a highly frustrated spin 1/2 Heisenberg chain with ferromagnetic nearest-neighbor and antiferromagnetic next-nearestneighbor interactions. The ESR data reveals that the significant magnetic anisotropy is due to anisotropy of the g-factor. Quantitative analysis of the critical broadening of the linewidth suggest appreciable interchain and interlayer spin correlations well above the ordering temperature. The Ni-based system is an organic-anorganic hybrid material where the Ni2+ ions possessing the integer spin S = 1 are magnetically coupled along one spatial direction. Indeed, the ESR study reveals an isotropic spin-1 Heisenberg chain in this system which unlike the Cu half integer spin-1/2 chain is expected to possess a qualitatively different non-magnetic singlet ground state separated from an excited magnetic state by a so-called Haldane gap. Surprisingly, in contrast to the expected Haldane behavior a competition between a magnetically ordered ground state and a potentially gapped state is revealed. In Part III investigations on SiGe/Si quantum dot structures are presented. The ESR investigations reveal narrowlines close to the free electron g-factor associated with electrons on the quantum dots. Their dephasing and relaxation times are determined. Manipulations with sub-bandgap light allow to change the relative population between the observed states. On the basis of extensive characterizations, strain, electronic structure and confined states on the Si-based structures are modeled with the program nextnano3. A qualitative model, explaining the energy spectrum of the spin states is proposed.:Abstract i Contents iii List of Figures vi List of Tables viii 1 Preface 1 I Background and Experimental 5 2 Principles of ESR 7 2.1 The Resonance Phenomenon . . . . . . . . . . . . . . . . . . . 7 2.2 ESR Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2.2.1 The g -factor . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.2.2 Relaxation Times . . . . . . . . . . . . . . . . . . . . . . 12 2.2.3 Lineshape Properties . . . . . . . . . . . . . . . . . . . . 13 2.3 Effective Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . 15 2.4 Spin-Orbit Coupling . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.5 d-electrons in a Crystal Field . . . . . . . . . . . . . . . . . . . . 17 2.6 Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 2.6.1 Dipolar Coupling . . . . . . . . . . . . . . . . . . . . . . 23 2.6.2 Exchange Interaction . . . . . . . . . . . . . . . . . . . . 23 2.6.3 Superexchange . . . . . . . . . . . . . . . . . . . . . . . 24 2.6.4 Symmetric Anisotropic Exchange . . . . . . . . . . . . 25 2.6.5 Antisymmetric Anisotropic Exchange . . . . . . . . . . 25 2.6.6 Hyperfine Interaction . . . . . . . . . . . . . . . . . . . 26 3 Experimental 27 3.1 Setup for Experiments at 10GHz . . . . . . . . . . . . . . . . . 27 3.2 Implementation of an EDMR Setup . . . . . . . . . . . . . . . . 29 3.2.1 Basic Characterization . . . . . . . . . . . . . . . . . . . 31 3.3 High Frequency Setup . . . . . . . . . . . . . . . . . . . . . . . . 31 3.3.1 MillimeterWave Vector Network Analyzer . . . . . . . 33 3.3.2 Waveguides and Cryostats . . . . . . . . . . . . . . . . . 34 3.4 Development of the Resonant Cavity Setup . . . . . . . . . . . 35 3.4.1 Mode Propagation . . . . . . . . . . . . . . . . . . . . . 38 3.4.2 Resonant CavityModes . . . . . . . . . . . . . . . . . . 40 3.4.3 Resonant Cavity Design . . . . . . . . . . . . . . . . . . 41 3.4.4 Resonant Cavity Sample Stick . . . . . . . . . . . . . . . 45 3.4.5 Experimental Characterization . . . . . . . . . . . . . . 47 3.4.6 Performing an ESR Experiment . . . . . . . . . . . . . . 53 II Quasi One-Dimensional Spin-Chains 57 4 Motivation 59 5 Quasi One-Dimensional Systems 61 5.1 Magnetic Order and Excitations . . . . . . . . . . . . . . . . . . 63 5.2 Competing Interactions . . . . . . . . . . . . . . . . . . . . . . . 64 5.3 Haldane Spin Chain . . . . . . . . . . . . . . . . . . . . . . . . . 66 6 Linarite 69 6.1 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70 6.2 Magnetization and ESR . . . . . . . . . . . . . . . . . . . . . . . 71 6.3 NMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 6.4 Summary and Conclusion . . . . . . . . . . . . . . . . . . . . . 81 6.5 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 7 The Ni-hybrid NiCl3C6H5CH2CH2NH3 83 7.1 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 7.2 Susceptibility andMagnetization . . . . . . . . . . . . . . . . . 85 7.3 ESR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 7.4 Further Investigations . . . . . . . . . . . . . . . . . . . . . . . . 95 7.5 Summary and Conclusion . . . . . . . . . . . . . . . . . . . . . 96 8 Summary 99 III SiGe Nanostructures 101 9 Motivation 103 10 SiGe Semiconductor Nanostructures 107 10.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 10.1.1 Silicon and Germanium . . . . . . . . . . . . . . . . . . 107 10.1.2 Epitaxial Growth of SiGe Heterostructures . . . . . . . 109 10.1.3 Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 10.1.4 Band Deformation . . . . . . . . . . . . . . . . . . . . . 112 10.2 Sample Structure and Characterization . . . . . . . . . . . . . 114 11 Modelling of SiGe/Si Heterostructures 119 11.1 Program Structure . . . . . . . . . . . . . . . . . . . . . . . . . . 120 11.2 Implementation of Si/Ge System . . . . . . . . . . . . . . . . . 121 11.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 11.3.1 Single Quantum Dot . . . . . . . . . . . . . . . . . . . . 123 11.3.2 Multiple Quantum Dots . . . . . . . . . . . . . . . . . . 127 11.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130 11.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132 12 ESR Experiments on Si/SiGe Quantum Dots 135 12.1 ESR on Si Structures . . . . . . . . . . . . . . . . . . . . . . . . . 135 12.2 Experimental Results . . . . . . . . . . . . . . . . . . . . . . . . 137 12.2.1 Samples grown at 600◦C . . . . . . . . . . . . . . . . . . 138 12.2.2 Samples grown at 700◦C . . . . . . . . . . . . . . . . . . 139 12.2.3 T1-Relaxation Time . . . . . . . . . . . . . . . . . . . . . 143 12.2.4 Effect of Illumination . . . . . . . . . . . . . . . . . . . . 145 12.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148 12.3.1 Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . 149 12.3.2 Assignment of ESR Lines . . . . . . . . . . . . . . . . . . 150 12.3.3 Relaxation Times . . . . . . . . . . . . . . . . . . . . . . 153 12.3.4 Donors in Heterostructures . . . . . . . . . . . . . . . . 153 12.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156 13 Summary and Outlook 157 Bibliography 163 Acknowledgements 176

Since the last few decades frustrated spin systems have attracted much interest. These studies are motivated by the rich variety of their unusual magnetic properties and potential applications. In this thesis, excitation spectra of the weakly coupled dimer system Ba3Cr2O8, the spin-1/2 chain material with distorted diamond structure Cu3(CO3)2(OH)2 (natural mineral azurite), and the quasi-twodimensional antiferromagnet with triangle spin structure Cs2CuBr4 have been studied by means of high-field electron spin resonance. Two pairs of gapped modes corresponding to transitions from a spin-singlet ground state to the first excited triplet state with zero-field energy gaps, of 19.1 and 27 K were observed in Ba3Cr2O8. The observation of ground-state excitations clearly indicates the presence of a non-secular term allowing these transitions. Our findings are of crucial importance for the interpretation of the field-induced transitions in this material (with critical fields Hc1 = 12.5 T and Hc2 = 23.6 T) in terms of the magnon Bose-Einstein condensation. The natural mineral azurite, Cu3(CO3)2(OH)2, has been studied in magnetic fields up to 50 T, revealing several modes not observed previously. Based on the obtained data, all three critical fields were identified. A substantial zero-field energy gap, Δ = 9.6 K, has been observed in Cs2CuBr4 above the ordering temperature. It is argued that contrary to the case for the isostructural Cs2CuCl4, the size of the gap can not be explained solely by the uniform Dzyaloshinskii-Moriya interaction, but it is rather the result of the geometrical frustration stabilizing the spin-disordered state in Cs2CuBr4 in the close vicinity of the quantum phase transition between a spiral magnetically ordered state and a 2D quantum spin liquid.

Conventional computing faces a huge technical challenge as traditional transistors will soon reach their size limitations. This will halt progress in reaching faster processing speeds and to overcome this problem, require an entirely new approach. Quantum computing (QC) is a natural solution offering a route to miniaturisation by, for example, storing information in electron or nuclear spin states, whilst harnessing the power of quantum physics to perform certain calculations exponentially faster than its classical counterpart. However, QCs face many difficulties, such as, protecting the quantum-bit (qubit) from the environment and its irreversible loss through the process of decoherence. Hybrid systems provide a route to harnessing the benefits of multiple degrees of freedom through the coherent transfer of quantum information between them. In this thesis I show coherent qubit transfer between electron and nuclear spin states in a ¹⁵N@C₆₀ molecular system (comprising a nitrogen atom encapsulated in a carbon cage) and a solid state system, using phosphorous donors in silicon (Si:P). The propagation uses a series of resonant mi- crowave and radiofrequency pulses and is shown with a two-way fidelity of around 90% for an arbitrary qubit state. The transfer allows quantum information to be held in the nuclear spin for up to 3 orders of magnitude longer than in the electron spin, producing a ¹⁵N@C₆₀ and Si:P ‘quantum memory’ of up to 130 ms and 1.75 s, respectively. I show electron and nuclear spin relaxation (T₁), in both systems, is dominated by a two-phonon process resonant with an excited state, with a constant electron/nuclear T₁ ratio. The thesis further investigates the decoherence and relaxation properties of metal atoms encapsulated in a carbon cage, termed metallofullerenes, discovering that exceptionally long electron spin decoherence times are possible, such that these can be considered a viable QC candidate.