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<p>This thesis is the result of several experiments designed to probe the low temperature physics underlying the 1D-Ising-like behaviour of chains of spins in the structure of Cobalt Niobate, CoNb2O6. A collection of prior work has been done by several groups prior to this, focusing on mapping the phase diagram above 0.5K. Interest in this material was renewed recently based upon theoretical work and experimental confirmation of the unique structure of the spins in the system. The bulk of this work was done at temperatures below the previously investigated range to probe the unique properties of this system.</p> <p>The material was grown at McMaster University using the optical floating zone technique from oxide powders. The crystal was examined and oriented using single crystal and Laue diffraction and was cut for use in further experiments. Squid magnetometry was used to confirm the material properties and phase transition temperatures, and was compared to literature values.</p> <p>Heat capacity measurements were performed locally down to 2K, and by collaborators at Waterloo in the range from 330mK to 1K. The heat capacity measurement confirmed the 2.9K transition and explored the relaxation time of the material. Cobalt niobate was found to have an exceptionally long relaxation time at low temperatures indicating strong spin-spin interactions. A sharp transition with zero applied field was found to become a broad, smooth feature at 2.9K when a small field was applied.</p> <p>We performed muSR measurements in zero, longitudinal and transverse field. The muSR results confirmed the long relaxation time found by the heat capacity measurements, which may reflect the coupling of the spin system to the lattice. Additionally, the material was never seen to statically order in zero or longitudinal field down to 700mK and up to 1T. The material was found to behave dynamically throughout all the field ranges.</p> / Master of Science (MSc)

This thesis contains the results of the extensive study into the synthesis of nickel niobate (NiNb2O6) including the formation of what was a previously unreported polymorph of the material, as well as the magnetic properties of both cobalt niobate (CoNb2O6) and nickel niobate using techniques including SQUID magnetometry, powder and single crystal x-ray scattering, powder and single crystal neutron scattering and muon spin rotation/relaxation. In cobalt niobate we found extremely long relaxation times in the heat capacity which showed up strongly in muon spin rotation experiments but not in neutron measurements. Additionally, with field applied to the system we see the emergence of spin-wave like structures in the neutron scattering data. Within cobalt niobate the strongest interaction is ferromagnetic and along the chain. The chains themselves are laid out on a triangular fashion and interact, although far more weakly, in an antiferromagnetic manner. This triangular patterning as well as an antiferromagnetic interaction results in interchain frustration, which protects the quasi-1D nature of the system due to the difficulty generated in creating 3D order. In nickel niobate we found that growth conditions caused highly variable changes, and we were able to create two different polymorphs. One polymorph was in the same space group as cobalt niobate, which gave us an opportunity to explore the magnetic difference between a spin-½ and spin-1 magnetic system and in nickel niobate in the new space group we performed an ab initio characterization solving the unit cell structure, the magnetic structure with neutron scattering as well as a magnetic characterization with SQUID magnetometry and muon spin rotation, allowing us to contrast the significant crystallographic differences. For the new polymorph we were able to determine its magnetic structure, characterized by Ising-like spins arranged in frustrated tetrahedra with three of the four points lying in the same plane as the spin, and for both materials we were able to use zero-field μSR data to estimate behaviour near the critical point and determine a critical exponent near the magnetic transitions. In both polymorphs there is evidence of constrained magnetism or reduced dimensionality, although the evidence for low dimensionality is much stronger in the columbite polymorph. / Thesis / Doctor of Philosophy (PhD) / This thesis examines two different niobium-based compounds: cobalt niobate (CoNb2O6) and nickel niobate (NiNb2O6). In these systems the cobalt and nickel atoms provide interesting magnetic properties. Within a magnetic material, the magnetic atoms tend to have their spins align in certain ways. The atoms themselves are fixed to particular sites by the way the material is assembled; an atomic framework. In the case of cobalt niobate, the magnetic atoms are arranged in well-separated chains so that a magnetic atom interacts strongly with its magnetic neighbours within a chain, and weakly with ones that are further away. This is an example of a material that is called `low dimensional'. The chains themselves form triangular patterns, and the interactions between chains are both weaker and antialigned, which creates a frustrated competition between the chains, protecting the low dimensional state by creating conditions where it is hard for all the spins in the material to order. For nickel niobate, the magnetic moments all want to anti-align, or be pointing in the opposite direction as its nearest neighbour. The magnetism is `frustrated' because each magnetic atom is tetrahedrally connected to three other atoms, so it cannot meet that condition. This can be visualized by drawing a triangle and trying to make each corner have an arrow pointing up or down. The third corner of the triangle cannot satisfy this requirement for its neighbours (one up and one down arrow). Both decreased dimensionality and frustration can lead to the emergence of novel quantum states of matter at low temperature. This thesis explores these materials with that in mind.

Litiumjonbatterier (LIB) är viktiga komponenter i dagens teknologi och används för att driva en mängd olika elektroniska system, allt från datorer och mobiltelefoner till bilar och flygplan. Eftersom efterfrågan på effektiv energilagring fortsätter att växa finns ett fortsatt behov för forskning och utveckling inom området. Denna rapport undersöker hårt kol, ett lovande material för anoder i litiumjonbatterier och andra alkali-jon batterier. I likhet med grafit är hårt kol ett kolbaserat material som inte är en väldefinierad allotropp utan en komplex blandning med avseende på både hybridiseringstillstånd och långdistansordning.  Därför är den mycket dåligt definierat. Ändå är hårt kol ett önskvärt material eftersom det kan produceras från förnybara resurser samt på grund av dess kompatibilitet med natrium, vilket möjliggör natriumjonbatterier. I den här studien har elektroder av hårt kol syntetiserats och litierats i olika grader och sedan studerats med 7Li NMR-spektroskopi där både spektra och longitudinella relaxationshastigheter mättes. Vid lägre litieringsnivåer observerades tydliga smala 7Li toppar inom intervallet 4-16 ppm, vilket indikerar förekomsten av joniskt litium. Vid högre litieringsnivåer framträdde en bred topp vid 61 ppm. Utseendet av denna topp, tillsammans med en hög Knight-skift, indikerar närvaron av kvasi-metalliskt litium. Det är värt att notera att detta kvasi-metalliska litium finns i de oordnade och porösa områdena hos hård kol. 7Li longitudinella relaxationshastigheter, som rapporterar om jonisk dynamik, registrerades vid olika temperaturer och från det observerade temperaturberoendet beräknades den genomsnittliga aktiveringsenergin för de involverade joniska rörelserna. Intressant nog visade sig denna aktiveringsenergi vara lägre jämfört med den i PAN-baserade kolfibrer och grafit, som båda uppvisar en högre grad av ordning. Denna observation tyder på ett samband mellan lokal oordning och snabbare jondynamik. / Lithium-ion batteries (LIB) are vital components of modern technology, powering a wide range of devices from computers and cell phones to cars and aeroplanes. As the demand for efficient energy storage continues to grow, research and development in the field of lithium-ion batteries remain active. This report focuses on the investigation of hard carbon, a promising anode material for lithium-ion batteries and other alkali-ion batteries. Akin to graphite, hard carbon is a carbon-based material that is not a well-defined allotrope but a complex mixture with regard to both hybridization state and long-range order. Hence it is very poorly defined. Yet, hard carbon is a desirable material as it can be produced from renewable resources and because of its compatibility with sodium, allowing for sodium-ion batteries. In this study, hard carbon electrodes were synthesised and lithiated to various degrees and then studied with 7Li NMR spectroscopy where both spectra and longitudinal relaxation rates were measured.   At lower lithiation levels, distinct narrow 7Li peaks were observed within the 4-16 ppm range, indicating the presence of ionic lithium. At higher lithiation levels a broad peak at 61 ppm emerged. The appearance of this peak, along with a high Knight shift, signifies the presence of quasi-metallic lithium, presumably in the more disordered and more porous regions of hard carbon. The 7Li longitudinal relaxation rates, reporting on ionic dynamics, were recorded at different temperature and from the observed temperature dependence the average activation energy for the involved ionic motions was calculated. Interestingly, this activation energy was found to be lower compared to that for PAN-based carbon fibres and graphite, both of which exhibit a higher degree of order. This observation suggests a correlation between local disorder and faster ion dynamics.

This dissertation focuses on projects where optical techniques were employed to characterize novel materials, developing concepts toward next generation of devices. The materials that I studied included InAsP, InMnSb and InMnAs, and BT-BCN. I have employed several advanced time resolved and magneto-optical techniques to explore unexplored properties of these structures. The first class of the materials were the ternary alloys InAsP. The electron g-factor of InAsP can be tuned, even allowing for g=0, making InAsP an ideal candidate for quantum communication devices. Furthermore, InAsP shows promises for opto-electronics and spintronics, where the development of devices requires extensive knowledge of carrier and spin dynamics. Thus, I have performed time and polarization resolved pump-probe spectroscopy on InAsP with various compositions. The carrier and spin relaxation time in these structures were observed and demonstrated tunability to the excitation wavelengths, composition and temperature. The sensitivity to these parameters provide several avenues to control carrier and spin dynamics in InAsP alloys. The second project focused on the ferromagnetic narrow gap semiconductors InMnAs and InMnSb. The incorporation of Mn can lead to ferromagnetic behavior of InMnAs and InMnSb, and enhance the g-factors, making them ideal candidates for spintronics devices. When grown using Molecular Beam Epitaxy (MBE), the Curie temperature (textit{$T_c$}) of these structures is textless 100 K, however structures grown using Metalorganic Vapor phase Epitaxy (MOVPE) have textit{$T_c$} textgreater 300 K. Magnetic circular dichroism was performed on MOVPE grown InMnAs and InMnSb. Comparison of the experimental results with the theoretical calculations provides a direct method to map the band structure, including the temperature dependence of the spin-orbit split-off band to conduction band transition and g-factors, as well as the estimated sp-d electron/hole coupling parameters. My final project was on the lead-free ferroelectric BT-BCN. Ferroelectric materials are being investigated for high speed, density, nonvolatile and energy efficient memory devices; however, commercial ferroelectric memories typically contain lead, and use a destructive reading method. Reflectometry measurements were used in order to determine the refractive index of BT-BCN with varying thicknesses, which can provide a means to nondestructively read ferroelectric memory through optical methods. / Ph. D. / This dissertation focuses on the characterization of materials that are important for the next generation computer architecture through optical techniques. These materials include the ternary alloy InAsP, the ferromagnetic semiconductors InMnAs and InMnSb, and the lead-free ferroelectric BT-BCN. InAsP is a ternary alloy composed of the technologically important InAs and InP, and by changing the alloy composition, the band gap and g-factor can be tuned. This allows for InAsP to have band gaps within the communication band, which is important for fiber optic communications as well as infrared photodetectors. As the functionality of these devices depends on the carrier dynamics, I have performed pump-probe spectroscopy in order to probe the carrier and spin relaxation times of this material system. These relaxation times were found to vary with excitation wavelengths, allowing flexibility in the application of this material system for devices. InAs and InSb are attractive materials for device applications because they offer large electron g-factor, small effective masses, and high mobilities. With the incorporation of Mn, these materials can become ferromagnetic, allowing for their use in ferromagnetic memories as well as other possible devices. The theory of ferromagnetism in semiconductors relies on the interaction between the itinerant holes and the Mn ions, however, in narrow gap semiconductors there is a large band mixing between the conduction and valence band states, and thus the interaction between the conduction band electrons and the Mn is important. In this study, my measurements revealed several interband transitions, which allowed for the calculation of the coupling constants between the electrons, holes and the Mn. My final study involved the lead-free ferroelectric BT-BCN. Ferroelectric materials are ideal for fast, low power and nonvolatile memories; however, typical implementation utilizes materials that contain lead, and a destructive reading mechanism, requiring a rewrite step. Optical, nondestructive reading methods are being explored based off of the rotation of the polarization of light as it passes through the sample. As this requires knowledge of the refractive index, I performed reflectometry measurements in order to determine the refractive indices of several BT-BCN films.

L'imagerie par résonance magnétique (IRM) est un outil remarquable pour le diagnostic clinique, aussi bien pour l'imagerie cérébrale que pour l'imagerie cardiaque et abdominale. En IRM cardiaque, deux problèmes sont récurrents : la non reproductibilité des cycles cardiaques et le mouvement respiratoire. L'IRM cardiaque morphologique est généralement faite avec une séquence composée d'une préparation longue, visant à annuler le signal du sang pour accentuer le contraste au niveau du myocarde, et de l?acquisition à proprement parler. Ces acquisitions sont généralement faites en mésodiastole (phase de relaxation passive du coeur) ce qui permet de satisfaire les contraintes liées à l'annulation du sang et d'éviter les problèmes liés aux non reproductibilités des cycles cardiaques car la mésodiastole est longue. Il est donc difficile de satisfaire les contraintes liées à l?annulation du sang pour faire les acquisitions en télésystole (phase où le coeur est contracté) à cause des non reproductibilités cardiaques car la télésystole est courte. Afin de passer outre ces limitations et de pouvoir acquérir ces mêmes images morphologiques en télésystole, nous proposons une nouvelle méthode adaptative qui permet à la fois de placer la fenêtre d'acquisition de manière optimale et de satisfaire les contraintes liées à l'annulation du sang. Une application de cette méthode a également été mise en place pour estimer et comparer les temps de relaxation transversale (T2) entre télésystole et mésodiastole. Pour la gestion prospective du mouvement respiratoire, le point crucial est d'estimer les mouvements en temps réel en perturbant au minimum les signaux de résonance magnétique. Pour ce faire nous proposons une méthode basée sur l'estimation paramétrique des mouvements en temps réel à partir des signaux physiologiques disponibles (ceintures respiratoires et ECG). Cette méthode a été testée et les résultats montrent son intérêt et sa fiabilité par rapport aux erreurs faites au niveau du mouvement. Une méthode de reconstruction incluant les mouvements a également été utilisée pendant ces travaux afin de faire de l'imagerie en télésystole en respiration libre et d'utiliser d'autres types de capteurs respiratoires comme certains signaux de résonance magnétique. Ainsi pendant ces travaux, des méthodes adaptatives ont été mises en place afin de mieux gérer le mouvement et de prendre en compte les spécificités de chaque patient. Ces travaux ouvrent la voie de l'imagerie par résonance magnétique adaptative pleinement fonctionnelle dans un contexte clinique / Magnetic resonance imaging (MRI) is a valuable tool for the clinical diagnosis for brain imaging as well as cardiac and abdominal imaging. In cardiac MRI, there are two challenging issues: the non reproducibility of cardiac cycles and respiratory motion. Morphological cardiac MRI is generally performed with a pulse sequence composed of a long preparation, to cancel the blood signal and thus enhance the contrast of the myocardium, and the acquisition itself. These acquisitions are performed during the mid-diastolic rest (relaxation period of the heart) to satisfy constraints to cancel the blood signal and to avoid problems linked to the cardiac non reproducibility because the mid-diastolic rest is long. Consequently, to acquire images in end-systolic rest (when the heart is fully contracted) while taking into account constraints to cancel the blood signal is not straight forward due to cardiac non reproducibility because the end-systolic rest is short. To overcome these limitations and to acquire images in end-systolic rest, a new adaptive method is introduced that allows to optimally placing acquisition windows while taking constraint for the cancellation of the blood signal into account. This method was applied to measure and compare transverse relaxation time (T2) between end-systolic and mid-diastolic rests. For prospective respiratory motion correction, the crucial point is to estimate motion in real-time without perturbing MR signal used for imaging. In order to solve this issue, a new method is introduced aiming at estimating motion parameters in real-time based on physiological signals such as respiratory bellows and ECG. This method is evaluated and results show its interest and its reliability regarding motion estimation errors. A reconstructions algorithm is also used in order to perform cardiac imaging during the end-systolic rest in free breathing and to use different kind of respiratory motion sensors such as MR signals. Hence, during this research work, several adaptive method were developed to get a better management of motion and to take into account specificity of each patient. These works open the way of fully functional adaptive magnetic resonance imaging in a clinical situation

Diese Dissertation besteht aus zwei Teilen von Studien. Der erste Teil demonstriert die Steuerung der Elektron-Kern-Spin-Systems in II-VI Halbleiter Quantum Dots (QDs) durch elektrische Ströme über Mikrospulen. Mikrometer-große Leiterschleifen sind auf der Oberseite von Heterostrukturen mit geladenen CdSe/ZnS QDs hergestellt worden. Eine Strominjektion erzeugt magnetische Felder im Bereich von einige 10 mT, welche stark genug sind, um die Hyperfeinwechselwirkung in CdSe QDs modulieren zu können. Der Durchmesser des Spulen im Mikrometer-Bereich ermöglicht die Generation von schnellen Feld transienten im Bereich von wenigen ns. Mit diesen Vorteilen der Mikrospulen werden die Steuerungs des Spins der residenten Elektronen sowie das Auslesen des Kernspinzustandes durch elektrische Impulse nachgewiesen. Der zweite Teil befasst sich mit der Ladungsträger-Spindynamik in ZnO Quantum Well (QW) Strukturen und Epitaxieschichten, die mittels des optischen Übergang von negativ geladenen Exzitonen X− beziehungsweise des am neutralen Donator gebunden Exziton D0X untersucht werden. Der Loch-Spin kann direkt über die zirkular polarisierten Photolumineszenz der beiden Komplexe zurückverfolgt werde. Die Spin-Relaxationszeit von QW und Epiplyer verfolgt werden. Der Spin des Donatorelektronens wird über die Ausbleichung des Spin-selektive Anregungprozesses nachgewiesen. Es werden longitudinale Loch-Spinrelaxationszeiten von 80 bis 140 ps für D0X und X− gefunden. Deutlich längere longitudinalen Elektronen-Spin-Relaxationszeiten in Bereich von mehreren 100 ns werden gefunden, wenn die Hyperfeinwechselwirkung durch ein geeignetes externes Magnetfeld unterdrückt wird. Eine Feldstärke von 2 mT ist groß genug. Dies zeigt den extrem kleinen Wert des Overhauser-Feldes in ZnO auf, der durch die sehr begrenzte Anzahl von magnetischen Kernen in Wechselwirkung mit dem Elektronen innerhalb des Volumens des Donators verursacht wird. / This work is composed of two parts of studies. The first part represents an electron-nuclear spin control in II-VI semiconductor quantum dots (QDs) by electrical currents via micro coils. Micrometer single turn coils are fabricated on top of heterostructures with charged CdSe/ZnSe QDs. Current injection creates magnetic fields in the range of some 10 mT which is strong enough to modulate the hyperfine interaction in CdSe. The micrometer-range diameter of coil allows for generation of fast field transient in the range of few ns. Using these advantages of micro coils, local control of the resident electron spin as well as read out of the nuclear spin state are demonstrated by electrical pulses. The second part presents charged carrier spin dynamics in ZnO quantum wells and epilayers using the optical transition of the negatively charged exciton X− and the neutral donor bound exciton D0X, respectively. The hole spin can be directly traced by the circular polarized photoluminescence of both complexes. The spin relaxation of the resident electrons and donor electrons is accessed via the bleaching of the spin selective excitation process. Longitudinal hole spin relaxation times of 80 and 140 ps are found for D0X and X−, respectively. Much longer longitudinal electron spin relaxation times in the several 100 ns range are uncovered if the hyperfine interaction is suppressed by a proper external magnetic field. A field strength of 2 mT is large enough proving that the extremely small value of the Overhauser field in ZnO caused by the very restricted number of magnetic nuclei interacting with the electron inside the donor volume.

Magnetic resonance imaging is a routine and powerful diagnostic technique capable of providing detailed information about the structure and composition of the tissues. This diploma thesis is concerned with the mechanisms of contrast origin and contrast modifications by molecular and nanoparticle contrast agents. First sections of the thesis summarize basic knowledge about pulse sequences and it aims to provide an overview on MRI contrast agent with a special emphasis on paramagnetic gadolinium contrast agents and superparamagnetic nanoparticles. The main purpose of this study is to develop the software called MRICalc, which is able to optimize contrast in MRI images. Based on analysis of signal formula of typical pulse sequences, MRICalc is able to propose the parameters of the pulse sequence for compartment-specific enhancement of the contrast. User chooses from the list of the samples and after calculation he obtains the values of echo time, repetition time and flip angle, all of which simultaneously seem to create the appropriate setting to enhance the contrast. MRICalc also allows to plot contrast function with respect to the chosen parameter. Software, including its graphical user interface, is designed in Python. The sample consists from solution of CuSO4 and distilled water was designed to verify the correct function of MRICalc. Sulphate represents a contrast agent. Preclinical MR system Bruker BioSpec 94/30 USR located at Institute of Scientific Instruments of the ASCR, v.v.i was used to measure contrast curve of FLASH pulse sequence, which is a typical representative of gradient echo. Results of the measurement were compared to the theoretical model provided by MRICalc.

Temperature-sensitive polymers or "smart" polymers are materials that undergo phase separation initiated by temperature change. Some of these polymers possess phase separation temperatures close to human body temperature (37 C), thus offering a wide range of potential applications in controlled drug release or gene delivery systems, bioseparations, tissue engineering, etc. Of the polymers with a phase separation temperature close to 37 C, poly(N- isopropylacrylamide) (PNIPAM) and poly(vinyl methyl ether) (PVME) are perhaps the most important and were selected as the subjects of this study. In this work, these two polymers have been examined in the presence of low molecular weight additives, and their colloidal stability evaluated using 1 H NMR (nuclear magnetic resonance) and time-resolved 1 H NMR spin-spin relaxation time T2 experiments. An improved model of the two exchangeable states was applied for a more detailed characterization of the phase separation process. The main focus of this study was to determine the influence of additives on the phase separation behavior of the polymers (phase separation temperature, width of transition, maximum number of polymer chains participating in phase separation), reversibility of the phase separation, dynamics of solvent molecules (water and additive),...

In this thesis, I study the electronic and structural phase diagrams of the superconducting 122 iron pnictides systems Ba1-xKx(Fe1-yCoy)2As2 and EuFe2(As1-xPx)2 by means of the local probe techniques 57Fe Mössbauer spectroscopy (MS) and muon spin relaxation (muSR). For both isovalent substitution strategies - Co/K for Fe/Ba and P for As, respectively - the antiferromagnetic Fe ordering and orthorhombic distortion of the parent compounds BaFe2As2 and EuFe2As2 are subsequently suppressed with increasing chemical substitution and superconductivity arises, once long-range and coherent Fe magnetic order is sufficiently but not entirely suppressed. For Ba1-xKx(Fe1-yCoy)2As2 in the charge compensated state (x/2=y), a remarkably similar suppression of both, the orthorhombic distortion and Fe magnetic ordering, as a function of increasing substitution is observed and a linear relationship between the structural and the magnetic order parameter is found. Superconductivity is evidenced at intermediate substitution with a maximum Tsc of 15 K coexisting with static magnetic order on a microscopic length scale. The appearance of superconductivity within the antiferromagnetic state can by explained by the introduction of disorder due to nonmagnetic impurities to a system with a constant charge carrier density. Within this model, the experimental findings are compatible with the predicted s± pairing symmetry. For EuFe2(As1-xPx)2, the results from 57Fe MS and ZF-muSR reveal an intriguing interplay of the local Eu 2+ magnetic moments and the itinerant magnetic Fe moments due to the competing structures of the iron and europium magnetic subsystems. For the investigated single crystals with x=0.19 and 0.28, 57Fe MS evidences the interplay of Fe and Eu magnetism by the observation of a transferred hyperfine field below Tafm at which the Eu subsystem orders into a canted A-type AFM magnetic structure. Furthermore, an additional temperature dependent out-of-plane tilting of the static Fe hyperfine field is observed below the onset of static Eu ordering. ZF-muSR shows a strong increase of the local field at the muon site below Tafm=20 K and a crossover from isotropic to anisotropic Eu spin-dynamics between 30 and 10 K. The temperature dependence of the spin dynamics, as derived from the muSR dynamic relaxation rates, are related to a critical slowing down of Eu-spin fluctuations which extends to even much higher temperatures (~100 K). They also effect the experimental linewidth observed in the 57Fe MS experiments. The strong influence of the Eu magnetic order onto the primary observables in both methods prevents conclusive interpretation of the experimental data with respect to a putative interplay of Fe magnetism and superconductivity.