Growth and characterisation of uranium multilayers.

This thesis investigates the extents of the 5f-3d and 5f-4f electronic interactions in U/Fe, U/Co and U/Gd thin films, where electronic hybridisation effects are expected to influence the magnetism of the U 5f states. The samples were prepared by DC magnetron sputtering and included niobium buffer and capping layers to instigate crystalline growth and prevent oxidation of the multilayer stack. Layer thicknesses were varied between 5A and 90A with up to 30 bilayer repeats. The majority of the samples were grown at room temperature, but selected compositions were grown at elevated substrate temperatures. Many well-defined Bragg peaks were evident in the X-ray reflectivity spectra of multilayers of all three systems, indicating a low impurity contamination and a well-reproduced bilayer structure. High-angle X-ray diffraction spectra of the transition metal multilayers revealed poorly crystalline, oriented transition metal layers with a non-crystalline component of Fe and Co of 17A. U/Gd X-ray diffraction spectra displayed intensities up to two orders of magnitude greater than those observed for U/Fe or U/Co samples of similar composition and contained satellite peaks, indicating some degree of coherency between the two species. An intense peak was observed, arising from a crystalline uranium component at a position close to that expected for an exotic hep U phase, oriented in the 001 direction. Bulk magnetisation measurements revealed magnetically 'dead' Fe and Co layers of 15A and magnetic moments tending towards the bulk values of 2.2/zb and 1.7/iB for thick Fe and Co layers respectively. A study of the bulk magnetic properties of the U/Gd system did not indicate the presence of any significant 'dead' layer, but reported a saturation magnetic moment for thick Gd layers of 4.5//b> considerably reduced from the bulk value of 7.63//B- Calculations of the magnetic anisotropy for U/Gd samples revealed a possible transition from the gadolinium moments aligned within the plane of the film to samples displaying perpendicular magnetic anisotropy (PMA), at a gadolinium layer thickness of 5A. This transition could be achieved for thicker Gd layers if the thickness of the U layers were increased. A finite-size scaling effect was observed in a gadolinium layer thickness dependent study of the Curie temperature, indicating a transition from three to two dimensional behaviour for very thin Gd layers. Polarised neutron reflectivity spectra were taken in the specular geometry at magnetic saturation, and were simulated with separate, reduced moment and bulk moment ferromagnetic layers for U/Fe and U/Co samples and a simple bilayer structure for U/Gd samples. This simultaneous measurement of both the physical composition and bulk magnetisation measurements supported results obtained by X-ray reflectivity and magnetometry. The hybridisation of the electronic states in U/Fe and U/Gd resulted in an induced polarisation, detected using element selective techniques. X-ray magnetic circular dichroism measurements at the U Mrv and My edges were used to investigate the spin and orbital components of the uranium magnetic moment and a total magnetic moment on the U site of 0.1/b for the case of U/Fe multilayers, 0.01/zb in U/Gd samples and a signal only barely detectable above the statistical noise in the U/Co system were revealed. A uranium layer thickness dependent study of the magnetic moment values was used to indirectly deduce the profile of uranium magnetisation within the layers. X-ray resonant magnetic reflectivity measurements provided a depth dependent measure of the induced U 5f moment for selected U/Fe samples, which indicated a more complicated interfacial structure than that deduced by X- ray and neutron reflectivity techniques and showed that the majority of the U 5f moment was located at the interface region

Interaction between U/UO2 bilayers and hydrogen studied by in-situ X-ray diffraction

This paper reports experiments investigating the reaction of H$_{2}$ with uranium metal-oxide bilayers. The bilayers consist of $\leq$ 100 nm of epitaxial $\alpha$-U (grown on a Nb buffer deposited on sapphire) with a UO$_{2}$ overlayer of thicknesses of between 20 and 80 nm. The oxides were made either by depositing via reactive magnetron sputtering, or allowing the uranium metal to oxidise in air at room temperature. The bilayers were exposed to hydrogen, with sample temperatures between 80 and 200 C, and monitored via in-situ x-ray diffraction and complimentary experiments conducted using Scanning Transmission Electron Microscopy - Electron Energy Loss Spectroscopy (STEM-EELS). Small partial pressures of H$_{2}$ caused rapid consumption of the U metal and lead to changes in the intensity and position of the diffraction peaks from both the UO$_{2}$ overlayers and the U metal. There is an orientational dependence in the rate of U consumption. From changes in the lattice parameter we deduce that hydrogen enters both the oxide and metal layers, contracting the oxide and expanding the metal. The air-grown oxide overlayers appear to hinder the H$_{2}$-reaction up to a threshold dose, but then on heating from 80 to 140 C the consumption is more rapid than for the as-deposited overlayers. STEM-EELS establishes that the U-hydride layer lies at the oxide-metal interface, and that the initial formation is at defects or grain boundaries, and involves the formation of amorphous and/or nanocrystalline UH$_{3}$. This explains why no diffraction peaks from UH$_{3}$ are observed. {\textcopyright British Crown Owned Copyright 2017/AWE}Comment: Submitted for peer revie

Characterization of poly- and single-crystal uranium-molybdenum alloy thin films

Poly- and single-crystal thin films of U-Mo alloys have been grown both on glass and sapphire substrates by UHV magnetron sputtering. X-ray and Electron Backscatter Diffraction data indicate that for single-crystal U1-xMox alloys, the pure cubic uranium gamma-phase exists for x > 0.22 (10 wt.% Mo). Below 10 wt.% Mo concentration, the resulting thin film alloys exhibited a mixed alpha-gamma uranium phase composition

The malleability of uranium: manipulating the charge-density wave in epitaxial films

We report x-ray synchrotron experiments on epitaxial films of uranium, deposited on niobium and tungsten seed layers. Despite similar lattice parameters for these refractory metals, the uranium epitaxial arrangements are different and the strains propagated along the a-axis of the uranium layers are of opposite sign. At low temperatures these changes in epitaxy result in dramatic modifications to the behavior of the charge-density wave in uranium. The differences are explained with the current theory for the electron-phonon coupling in the uranium lattice. Our results emphasize the intriguing possibilities of producing epitaxial films of elements that have complex structures like the light actinides uranium to plutonium.Comment: 6 pages, 6 figure

Structural properties of epitaxial {\alpha}-U thin films on Ti, Zr, W and Nb

Thin layers of orthorhombic uranium ({\alpha}-U) have been grown onto buffered sapphire substrates by d.c. magnetron sputtering, resulting in the discovery of new epitaxial matches to Ti(00.1) and Zr(00.1) surfaces. These systems have been characterised by X-ray diffraction and reflectivity and the optimal deposition temperatures have been determined. More advanced structural characterisation of the known Nb(110) and W(110) buffered {\alpha}-U systems has also been carried out, showing that past reports of the domain structures of the U layers are incomplete. The ability of this low symmetry structure to form crystalline matches across a range of crystallographic templates highlights the complexity of U metal epitaxy and points naturally toward studies of the low temperature electronic properties of {\alpha}-U as a function of epitaxial strain