arXiv subjects

R. Springell

Publications and source records attributed to R. Springell.

At least 19 recordsLinked to original sources

arXiv2024

Anisotropic Resonant Scattering from uranium systems at the U M4 edge

We have conducted a series of scattering experiments at the uranium M4 absorption edge on low-symmetry uranium compounds (U2N3 and U3O8) produced as epitaxial films. At weak and forbidden reflections, we find a resonant signal, independent of temperature, with an energy dependence resembling the imaginary part of the scattering factor. Theory, using the FDMNES code, shows that these results can be reliably reproduced assuming that they originate from aspherical 5f electron charge distributions around the U nucleus. Such effects arise from the intrinsic anisotropy of the 5f shell and from the mixing of the 5f electrons of uranium with the outer 2p electrons of the anions. The good agreement between theory and experiment includes azimuthal scattering dependencies, as well as polarization states of the scattered photons. The methodology reported here opens the way for a deeper understanding of the role of the 5f electrons in the bonding in actinide compounds.

cond-mat.str-el↗

arXiv2023

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.

cond-mat.mtrl-sci↗

arXiv2023

A review of uranium-based thin films

Thin films based on silicon and transition-metal elements dominate the semiconducting industry and are ubiquitous in all modern devices. Films have also been produced in the rare-earth series of elements for both research and specialized applications. Thin films of uranium and uranium dioxide were fabricated in the 1960s and 1970s, but there was little sustained effort until the early 2000s. Significant programmes started at Oxford University (transferring to Bristol University in 2011), and Los Alamos National Laboratory (LANL) in New Mexico, USA. In this review we cover the work that has been published over the last ~20 years with these materials. Important breakthroughs occurred with the fabrication of epitaxial thin films of initially uranium metal and UO2, but more recently of many other uranium compounds and alloys. These have led to a number of different experiments that are reviewed, as well as some important trends. The interaction with the substrate leads to differing strain and hence changes in properties. An important advantage is that epitaxial films can often be made of materials that are impossible to produce as bulk single crystals. Examples are U3O8, U2N3 and alloys of U-Mo, which form in a modified bcc structure. Epitaxial films may also be used in applied research. They represent excellent surfaces, and it is at the surfaces that most of the important reactions occur in the nuclear fuel cycle. For example, the fuel-cladding interactions, and the dissolution of fuel by water in the long-term storage of spent fuel. To conclude, we discuss possible future prospects, examples include bilayers containing uranium for spintronics, and superlattices that could be used in heterostructures. Such applications will require a more detailed knowledge of the interface interactions in these systems, and this is an important direction for future research.

cond-mat.mtrl-sci↗

arXiv2021

Magnetic anisotropy in Fe/U and Ni/U bilayers

Magnetometry measurements of Fe/U and Ni/U bilayer systems reveal a non-monotonic dependence of the magnetic anisotropy for U thicknesses in the range 0 nm - 8 nm, with the Fe/U bilayers showing a more prominent effect as compared to Ni/U. The stronger response for Fe/U is ascribed to the stronger 3d-5f hybridization of Fe and U. This non-monotonic behaviour is thought to arise from quantum well states in the uranium overlayers. Estimating an oscillation period from the non-monotonic data, and comparing it to Density Functional Theory calculations, we find that wavevector matches to the experimental data can be made to regions of high spectral density in (010) and (100) cuts of the electronic structure of{\alpha}-U, consistent with the measured texture in the films. Unexpectedly, there are also indications of perpendicular magnetic anisotropy in a subset of Fe/U samples at relatively large U thickness.

cond-mat.mes-hall↗

arXiv2020

Tuneable Correlated Disorder in Alloys

Understanding the role of disorder and the correlations that exist within it, is one of the defining challenges in contemporary materials science. However, there are few material systems, devoid of other complex interactions, which can be used to systematically study the effects of crystallographic conflict on correlated disorder. Here, we report extensive diffuse x-ray scattering studies on the epitaxially stabilised alloy $\mbox{U}_{1-x}\mbox{Mo}_x$, showing that a new form of intrinsically tuneable correlated disorder arises from a mismatch between the preferred symmetry of a crystallographic basis and the lattice upon which it is arranged. Furthermore, combining grazing incidence inelastic x-ray scattering and state-of-the-art ab initio molecular dynamics simulations we discover strong disorder-phonon coupling. This breaks global symmetry and dramatically suppresses phonon-lifetimes compared to alloying alone, providing an additional design strategy for phonon engineering. These findings have implications wherever crystallographic conflict can be accommodated and may be exploited in the development of future functional materials.

cond-mat.mtrl-sci↗

arXiv2019

Synchrotron x-ray scattering of UN and U2N3 epitaxial films

We examine the magnetic ordering of UN and of a closely related nitride, U2N3, by preparing thin epitaxial films and using synchrotron x-ray techniques. The magnetic configuration and subsequent coupling to the lattice are key features of the electronic structure. The well-known antiferromagnetic (AF) ordering of UN is confirmed, but the expected accompanying distortion at Tn is not observed. Instead, we propose that the strong magneto-elastic interaction at low temperature involves changes in the strain of the material. These strains vary as a function of the sample form. As a consequence, the accepted AF configuration of UN may be incorrect. In the case of cubic a-U2N3, no single crystals have been previously prepared, and we have determined the AF ordering wave-vector. The AF Tn is close to that previously reported. In addition, resonant diffraction methods have identified an aspherical quadrupolar charge contribution in U2N3 involving the 5f electrons; the first time this has been observed in an actinide compound.

cond-mat.mtrl-sci↗

arXiv2018

Comparing the Corrosion of Uranium Nitride and Uranium Dioxide Surfaces with H2O2

Uranium mononitride, UN, is considered a potential accident tolerant fuel due to its high uranium density, high thermal conductivity, and high melting point. Compared with the relatively inert UO2, UN has a high reactivity in water, however, studies have not considered the significant effect of radiation, which is known to cause corrosion of UO2. This study uses 0.1 M H2O2 to simulate the effects of water radiolysis in order to compare the radiolytic corrosion rates of UO2, UN, and U2N3 thin films at room temperature. X-ray reflectivity was used to investigate the changes in film morphology as a function of H2O2 exposure time, allowing changes in film thickness and roughness to be observed on the Angstrom length-scale. Results showed significant differences between UO2, UN, and U2N3, with corrosion rates of 0.083(3), 0.020(4), and 0.47(8) A/s, respectively, showing that UN corrodes more slowly than UO2 in 0.1 M H2O2.

cond-mat.mtrl-sci↗

arXiv2018

The Role of Crystal Orientation in the Dissolution of UO$_2$ Thin Films

Epitaxial thin films have been utilised to investigate the radiolytic dissolution of uranium dioxide interfaces. Thin films of UO$_2$ deposited on single crystal yttria stabilised zirconia substrates have been exposed to water in the presence of a high flux, monochromatic, synchrotron x-ray source. In particular, this technique was applied to induce dissolution of three UO$_2$ thin films, grown along the principle UO$_2$ crystallographic orientations: (001), (110) and (111). Dissolution of each film was induced for 9 accumulative corrosion periods, totalling 270s, after which XRR spectra were recorded to observe the change in morphology of the films as a function of exposure time. While the (001) and (110) oriented films were found to corrode almost linearly and at comparable rates, the (111) film was found to be significantly more corrosion resistant, with no loss of UO$_2$ material being observed after the initial 90s corrosion period. These results distinctly show the effect of crystallographic orientation on the rate of x-ray induced UO$_2$ dissolution. This result may have important consequences for theoretical dissolution models, as it is evident that orientation dependence must be taken into consideration to obtain accurate predictions of the dissolution behaviour of UO$_2$.

cond-mat.mtrl-sci↗

arXiv2018

Epitaxial UN and $\alpha$-U$_2$N$_3$ Thin Films

Single crystal epitaxial thin films of UN and U$_2$N$_3$ have been grown for the first time by reactive DC magnetron sputtering. These films provide ideal samples for fundamental research into the potential accident tolerant fuel, UN, and U$_2$N$_3$, its intermediate oxidation product. Films were characterised using x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS), with XRD analysis showing both thin films to be [001] oriented and composed of a single domain. The specular lattice parameters of the UN and U$_2$N$_3$ films were found to be 4.895\,\AA{} and 10.72\,\AA{}, respectively, with the UN film having a miscut of 2.6\,$^\circ$. XPS showed significant differences in the N-1s peak between the two films, with area analysis showing both films to be stoichiometric.

cond-mat.mtrl-sci↗

arXiv2018

Study of phonons in irradiated epitaxial thin films of UO$_2$

We report experiments to determine the effect of radiation damage on the phonon spectra of the most common nuclear fuel, UO$_2$. We have irradiated thin ($\sim$ 300 nm) epitaxial films of UO$_2$ with 2.1 MeV He$^{2+}$ ions to 0.15 dpa and a lattice swelling of $\Delta$a/a $\sim$ 0.6 %, and then used grazing-incidence inelastic X-ray scattering to measure the phonon spectrum. We succeeded to observe the acoustic modes, both transverse and longitudinal, across the Brillouin zone. The phonon energies, in both the pristine and irradiated samples, are unchanged from those observed in bulk material. On the other hand, the phonon linewidths (inversely proportional to the phonon lifetimes), show a significant broadening when comparing the pristine and irradiated samples. This effect is shown to increase with phonon energy across the Brillouin zone. The decreases in the phonon lifetimes of the acoustic modes are roughly consistent with a 50 % reduction in the thermal conductivity.

cond-mat.mtrl-sci↗

arXiv2017

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}

cond-mat.mtrl-sci↗

arXiv2015

The importance of XY anisotropy in Sr2IrO4 revealed by magnetic critical scattering experiments

The magnetic critical scattering in Sr$_2$IrO$_4$ has been characterized using X-ray resonant magnetic scattering (XRMS) both below and above the 3D antiferromagnetic ordering temperature, T$_{\text{N}}$. The order parameter critical exponent below T$_{\text{N}}$ is found to be \beta=0.195(4), in the range of the 2D XYh$_4$ universality class. Over an extended temperature range above T$_{\text{N}}$, the amplitude and correlation length of the intrinsic critical fluctuations are well described by the 2D Heisenberg model with XY anisotropy. This contrasts with an earlier study of the critical scattering over a more limited range of temperature which found agreement with the theory of the isotropic 2D Heisenberg quantum antiferromagnet, developed to describe the critical fluctuations of the conventional Mott insulator La$_2$CuO$_4$ and related systems. Our study therefore establishes the importance of XY anisotropy in the low-energy effective Hamiltonian of Sr$_2$IrO$_4$, the prototypical spin-orbit Mott insulator.

cond-mat.str-el↗

arXiv2014

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.

cond-mat.str-el↗

arXiv2013

Slaving of the magnetic moment canting to the correlated oxygen rotation in Sr2IrO4 revealed by X-ray resonant scattering

Sr2IrO4 is a prototype of the class of Mott insulators in the strong spin-orbit interaction (SOI) limit described by a $J_{\mathrm{eff}}=1/2$ ground state. In Sr2IrO4, the strong SOI is predicted to manifest itself in the slaving of the canting of the magnetic moments to the correlated rotation by 11.8(1)$^{\circ}$ of the oxygen octahedra that characterizes its distorted layered perovskite structure. Using X-ray resonant scattering at the Ir $L_3$ edge we have measured accurately the intensities of Bragg peaks arising from different components of the magnetic structure. From a careful comparison of integrated intensities of peaks due to basal-plane antiferromagnetism, with those due to b-axis ferromagnetism, we deduce a canting of the magnetic moments of 12.2(8)$^{\circ}$. We thus confirm that in Sr2IrO4 the magnetic moments rigidly follow the rotation of the oxygen octahedra, indicating that, even in the presence of significant non-cubic structural distortions, it is a close realization of the $J_{\mathrm{eff}}=1/2$ state

cond-mat.str-el↗

arXiv2013

X-ray magnetic circular dichroism experiments and theory of transuranium Laves phase compounds

The actinide cubic Laves compounds NpAl2, NpOs2, NpFe2, and PuFe2 have been examined by X-ray magnetic circular dichroism (XMCD) at the actinide M4,5 absorption edges and Os L2,3 absorption edges. The XMCD experiments performed at the M4,5 absorption edges of Np and Pu allow us to determine the spectroscopic branching ratio, which gives information on the coupling scheme in these materials. In all materials the intermediate coupling scheme is found appropriate. Comparison with the SQUID data for NpOs2 and PuFe2 allows a determination of the individual orbital and spin magnetic moments and the magnetic dipole contribution mmd. The resulting orbital and spin magnetic moments are in good agreement with earlier values determined by neutron diffraction, and the values of mmd are non-negligible, and close to those predicted for intermediate coupling. There is a comparatively large induced moment on the Os atom in NpOs2 such that the Os contribution to the total moment per formula unit is ~30% of the total. The spin and orbital moments at the Os site are parallel, in contrast to the anti-parallel configuration of Os impurities in 3d ferromagnetic transition metals. Calculations using the LDA+U technique are reported. The ab initio computed XMCD spectra show good agreement with experimental spectra for small values (0-1eV) of the Hubbard U parameter, which underpins that 5f electrons in these compounds are relatively delocalized.

cond-mat.str-el↗

arXiv2012

Robustness of basal-plane antiferromagnetic order and the $J_{eff}=1/2$ state in single-layer iridate spin-orbit Mott insulators

The magnetic structure and electronic groundstate of the layered perovskite Ba2IrO4 have been investigated using x-ray resonant magnetic scattering (XRMS). Our results are compared with those for Sr2IrO4, for which we provide supplementary data on its magnetic structure. We find that the dominant, long-range antiferromagnetic order is remarkably similar in the two compounds, and that the electronic groundstate in Ba2IrO4, deduced from an investigation of the XRMS $L_3/L_2$ intensity ratio, is consistent with a $J_{eff}=1/2$ description. The robustness of these two key electronic properties to the considerable structural differences between the Ba and Sr analogues is discussed in terms of the enhanced role of the spin-orbit interaction in 5d transition metal oxides.

cond-mat.str-el↗

arXiv2012

Bulk properties and electronic structure of PuFeAsO

Here we present bulk property measurements and electronic structure calculations for PuFeAsO, an actinide analogue of the iron-based rare-earth superconductors RFeAsO. Magnetic susceptibility and heat capacity data suggest the occurrence of an antiferromagnetic transition at TN=50 K. No further anomalies have been observed down to 2 K, the minimum temperature that we have been able to achieve. Structural measurements indicate that PuFeAsO, with its more localized 5f electrons, bears a stronger resemblance to the RFeAsO compounds with larger R ions, than NpFeAsO does.

cond-mat.supr-con↗

arXiv2012

Negative thermal expansion and antiferromagnetism in the actinide oxypnictide NpFeAsO

A neptunium analogue of the LaFeAsO tetragonal layered compound has been synthesized and characterized by a variety of experimental techniques. The occurrence of long-range magnetic order below a critical temperature T_N = 57 K is suggested by anomalies in the temperature-dependent magnetic susceptibility, electrical resistivity, Hall coefficient, and specific heat curves. Below T_N, powder neutron diffraction measurements reveal an antiferromagnetic structure of the Np sublattice, with an ordered magnetic moment of 1.70(0.07) \mu_B aligned along the crystallographic c-axis. No magnetic order has been observed on the Fe sublattice, setting an upper limit of about 0.3 \mu_B for the ordered magnetic moment on the iron. High resolution x-ray powder diffraction measurements exclude the occurrence of lattice transformations down to 5 K, in sharp contrast to the observation of a tetragonal-to-orthorhombic distortion in the rare-earth analogues, which has been associated with the stabilization of a spin density wave on the iron sublattice. Instead, a significant expansion of the NpFeAsO lattice parameters is observed with decreasing temperature below T_N, corresponding to a relative volume change of about 0.2% and to an invar behavior between 5 and 20 K. First-principle electronic structure calculations based on the local-spin density plus Coulomb interaction and the local density plus Hubbard-I approximations provide results in good agreement with the experimental findings.

cond-mat.supr-con↗