A novel imaging modality is introduced, using Radio-Frequency Longitudinally Detected Electron Spin Resonance (RF-LODESR), capable of providing qualitative and semi-quantitative information on a variety of parameters reflecting physiological function, the most significant being tissue oxygenation. Effective spin-lattice (T_1e*) and spin-spin (T_2e*) electronic relaxation time maps of the abdomen of living 200 g rats were generated after intravenous administration of a triarylmethyl free radical (TAM). These maps were used to evaluate oxygen distribution. Differences between the liver, kidneys and bladder were noted. Conclusions were made regarding distribution, perfusion and excretion rate of the contrast medium. Ligature induced anoxia in the kidney was also visualised. LODESR involves transverse ESR irradiation with a modulated excitation and observing oscillations in the spin magnetisation parallel to the main magnetic field. The T_1e* and T_2e* maps were calculated from a set of LODESR signal phase images collected at different detection frequencies. Each phase image also provides qualitative information on tissue oxygen level without any further processing. Additionally, a new method is introduced for measuring T_1e, valid for inhomogeneous spectra, based on measuring the spectral area as a function of detection frequency. These methods present alternatives to the conventional transverse ESR linewidth-based oximetry methods, particularly for animal whole body imaging applications.

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

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.

Magnetic fields influence the rate and/or yield of chemical reactions that proceed via spin correlated radical pair intermediates. The field of spin chemistry centres around the study of such magnetic field effects (MFEs). This thesis is particularly concerned with the effects of the weak magnetic fields B₀ ~ 1mT relevant in the ongoing debates on the mechanism by which animals sense the geomagnetic field and on the putative health effects of environmental electromagnetic fields. Relatively few previous studies have dealt with such weak magnetic fields. This thesis presents several new theoretical tools and applies them to interpret experimental measurements. Chapter 1 surveys the development and theory of spin chemistry. Chapter 2 introduces the use of Tikhonov and Maximum Entropy Regularisation methods as a new means of analysing MARY field effect data. These are applied to recover details of the diffusive motion of reacting pyrene and N,N-dimethylaniline radicals. Chapter 3 gives a fresh derivation and appraisal of an approximate, semiclassical approach to MFEs. Monte Carlo calculations allow the elucidation of several "rules of thumb" for interpreting MFE data. Chapter 4 discusses recent optically-detected zero-field EPR measurements, adapting the gamma-COMPUTE algorithm from solid state NMR for their interpretation. Chapter 5 explores the role of RF polarisation in producing MFEs. The breakdown in weak fields of the familiar rotating frame approximation is analysed. Chapter 6 reviews current knowledge and landmark experiments in the area of animal magnetoreception. The origins of the sensitivity of European robins Erithacus rubecula to the Earth’s magnetic field are given particular attention. In Chapter 7, Schulten and Ritz’s hypothesis that avian magnetoreception is founded on a radical pair mechanism (RPM) reaction is appraised through calculations in model systems. Chapter 8 introduces quantitative methods of analysing anisotropic magnetic field effects using spherical harmonics. Chapter 9 considers recent observations that European robins may sometimes be disoriented by minuscule RF fields. These are shown to be consistent with magnetoreception via a radical pair with no (effective) magnetic nuclei in one of the radicals.