Isolation and Reactivity of Uranyl Superoxide.

The high radiation field associated with spent nuclear fuel (UIV O2 ) pellets produces an array of reactive radical species that impact the corrosion and formation of secondary alteration phases. Dioxygen radicals are important as radiolysis products, but the interaction between these reactive oxygen species and UVI O22+ and its effects on the resultant alteration phases is unclear. We report the first example of a UVI superoxide compound and explore its reactivity in the environments relevant to the storage of spent nuclear fuel. We utilized X-ray diffraction and Raman scattering techniques to demonstrate that the uranyl superoxide reacts with CO2 in air to afford a mixed uranyl peroxide/carbonate within 3 days, both in solution and under atmospheric conditions. An additional transformation occurs over the course of 3 months to form a potassium UVI carbonate (grimselite), which also occurs as an alteration product on Chernobyl corium. Our results demonstrate the presence and significance of the superoxide anion in the alteration of spent nuclear fuel and indicate the impact of uranyl superoxide chemistry on high prevalence of carbonate in the secondary phases of spent nuclear fuel.

Universal method for creating optically active nanostructures on layered materials.

The ability to form patterned surface nanostructures has revolutionized the miniaturization of electronics and led to the discovery of emergent behaviors unseen in macroscopic systems. However, the creation of such nanostructures typically requires multiple processing steps, a high level of technical expertise, and highly sophisticated equipment. In this work, we have discovered a simple method to create nanostructures with control size and positioning in a single processing step using a standard scanning electron microscope. The technique can be applied to a wide range of systems and was successful in every layered material tested. Patterned nanostructures were formed on graphite, topological insulators, novel superconductors, and layered transition metal dichalcogenides. The nanostructures were formed via the incorporation of carbon nanoparticles into the samples in a novel form of intercalation. It appears that the electron beam interacts with residual organic molecules available on the sample surface, making it possible for them to intercalate between the layers in their crystal structure and break down into carbon. These carbon nanoparticles have strong broad-wavelength interactions in the visible light range, making these nanostructures easily detectable in an optical microscope and of interest for a range of nanoscale electro-optical devices.

Observation of low energy Raman modes in twisted bilayer graphene.

Two new Raman modes below 100 cm(-1) are observed in twisted bilayer graphene grown by chemical vapor deposition. The two modes are observed in a small range of twisting angle at which the intensity of the G Raman peak is strongly enhanced, indicating that these low energy modes and the G Raman mode share the same resonance enhancement mechanism, as a function of twisting angle. The ~94 cm(-1) mode (measured with a 532 nm laser excitation) is assigned to the fundamental layer breathing vibration (ZO' mode) mediated by the twisted bilayer graphene lattice, which lacks long-range translational symmetry. The dependence of this mode's frequency and line width on the rotational angle can be explained by the double resonance Raman process that is different from the previously identified Raman processes activated by twisted bilayer graphene superlattice. The dependence also reveals the strong impact of electronic-band overlaps of the two graphene layers. Another new mode at ~52 cm(-1), not observed previously in the bilayer graphene system, is tentatively attributed to a torsion mode in which the bottom and top graphene layers rotate out-of-phase in the plane.

Electronic, magnetic, and structural properties of NiFeMnAl.

Half-metallic Heusler compounds have been extensively studied in the recent years, both experimentally and theoretically, for potential applications in spin-based electronics. Here, we present the results of a combined theoretical and experimental study of the quaternary Heusler compound NiFeMnAl. Our calculations indicate that this material is half-metallic in the ground state and maintains its half-metallic electronic structure under a considerable range of external hydrostatic pressure and biaxial strain. NiFeMnAl crystallizes in the regular cubic Heusler structure, and exhibits ferromagnetic alignment. The practical feasibility of the proposed system is confirmed in the experimental section of this work. More specifically, a bulk ingot of NiFeMnAl was synthesized in A2 type disordered cubic structure using arc melting. It shows a high Curie temperature of about 468 K and a saturation magnetization of 2.3µB/f.u. The measured magnetization value is smaller than the one calculated for the ordered structure. This discrepancy is likely due to the A2 type atomic disorder, as demonstrated by our calculations. We hope that the presented results may be useful for researchers working on practical applications of spin-based electronics.

Perpendicular magnetic anisotropy in half-metallic thin-film Co2CrAl.

Magnetocrystalline anisotropy (MCA) is one of the key parameters investigated in spin-based electronics (spintronics), e.g. for memory applications. Here, we employ first-principles calculations to study MCA in thin film full Heusler alloy Co2CrAl. This material was studied in the past, and has been reported to exhibit half-metallic electronic structure in bulk geometry. In our recent work, we showed that it retains a 100% spin-polarization in thin-film geometry, at CrAl atomic surface termination. Here, we show that the same termination results in a perpendicular magnetic anisotropy, while Co surface termination not only destroys the half-metallicity, but also results in in-plane magnetization orientation. In addition, for films thicker than around 20 nm the contribution from magnetic shape anisotropy may become decisive, resulting in in-plane magnetization orientation. To the best of our knowledge, this is one of the first reports of half-metallic thin-film surfaces with perpendicular magnetic anisotropy. This result may be of interest for potential nano-device applications, and may stimulate a further experimental study of this and similar materials.