A method to determine the defect structures in hyper-stoichiometric UO(2+x) using a combination of XRD and Raman spectroscopy has been developed. A sequence of phase transitions, from cubic to tetragonal symmetry, occurs with increasing degree of non-stoichiometry. This sequence proceeds from a cubic phase through an intermediate t''-type tetragonal (axial ratio c/a = 1) phase to a final t-type tetragonal (c/a not = 1) phase. Four distinct structural defect regions can be identified in the stoichiometry range, UO(2) to U(3)O(7): (i) a random point defect structure (x (in UO(2+x)) < or = 0.05); (ii) a non-stoichiometry region (0.05 < or = x < or = 0.15) over which point defects are gradually eliminated and replaced by the Willis 2:2:2 cluster; (iii) a mixture of Willis and cuboctahedral clusters (0.15 < or = x < or = 0.23); (iv) the cuboctahedral cluster (x > or = 0.23). The geometry and steric arrangement of these defects is primarily determined by the concentration of the excess-oxygen interstitials.

With the growing interest in low dimensional materials, MXenes have also attracted considerable attention recently. In this work, the thermal and electrical properties of oxygen-functionalized M2CO2 (M = Ti, Zr, Hf) MXenes are investigated using first-principles calculations. Hf2CO2 is determined to exhibit a thermal conductivity better than MoS2 and phosphorene. The room-temperature thermal conductivity along the armchair direction is determined to be 86.25~131.2 Wm−1 K−1 with a flake length of 5~100 μm. The room temperature thermal expansion coefficient of Hf2CO2 is 6.094 × 10−6 K−1, which is lower than that of most metals. Moreover, Hf2CO2 is determined to be a semiconductor with a band gap of 1.657 eV and to have high and anisotropic carrier mobility. At room temperature, the Hf2CO2 hole mobility in the armchair direction (in the zigzag direction) is determined to be as high as 13.5 × 103 cm2V−1s−1 (17.6 × 103 cm2V−1s−1). Thus, broader utilization of Hf2CO2, such as the material for nanoelectronics, is likely. The corresponding thermal and electrical properties of Ti2CO2 and Zr2CO2 are also provided. Notably, Ti2CO2 presents relatively lower thermal conductivity but much higher carrier mobility than Hf2CO2. According to the present results, the design and application of MXene based devices are expected to be promising.

Detecting and understanding the complex signatures of species for attribution of highly enriched uranium, HEU, is challenging even though these compounds have been intensively studied for 65 years. Attempts to obtain, for example, chemical speciation signatures on uranium oxides are frustrated by the presence of extremely diverse phases, complex structures, and their tendency to form solid solutions with the coexistence of many nonstoichiometric oxides. More importantly, the spectroscopic signatures of many of these oxides, using common techniques such as X-ray diffraction or Raman scattering, are remarkably similar with each other. On the other hand, the effort to understand the U−O system also exhibits some of the most intriguing and challenging properties in theoretical and computational chemistry. This is due to the spatial extent between localization and delocalization of the 5f orbitals of the uranium atom. In this article, spectroscopic ellipsometry (SE) measurements and a comparison of six fitting methods as well as theoretical calculations are combined to examine the intrinsic electronic structure and the corresponding band gap of uranium oxides to determine the chemical speciation in a ∼102 nm thick reactively sputtered uranium oxide film. The SE results reveal that the UO x film exhibits two absorption edges, a primary absorption edge slightly above 2.6 eV and a secondary absorption at 1.7−1.8 eV. The optical band gaps compared with the theoretical calculations performed on UO 2 , U 4 O 9 , U 3 O 7 , α-U 3 O 8 , α-UO 3 , δ-UO 3 , and γ-UO 3 suggest that the UO x film is composed of at least two components; the primary absorption is caused by the α-UO 3 sublayer, which is superimposed on top of an adjacent α-U 3 O 8 sublayer that is hypothesized to be heteroepitaxial growth of α-U 3 O 8 along the UO x /substrate interface. Comparison to the ellipsometry measurements shows that the DFT+U and hybrid (HSE) calculations predict the correct trend for band gaps as a function of oxidation state and crystallography but they fail to capture the exact gaps. However, they provide important information for interpretation of the experimental results and highlight some of the structural complexity that prevails in the UO x compounds. The combination of theoretical and experimental methods to examine the intrinsic electronic structure and the band gap of the corresponding uranium oxides could benefit from the development of new methods for better distinguishing chemical speciation in uranium oxides. In addition, the experimental measurement of the indirect band gap of α-U 3 O 8 , is, to our knowledge, reported for the first time.

The influence of fission product doping on the structure, composition, and electrochemical reactivity of uranium dioxide has been studied using X-ray diffractometry (XRD), scanning electron microscopy (SEM/EDX), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Experiments were conducted on SIMFUEL specimens with simulated burn-ups (increasing doping levels) of 1.5, 3.0, and 6.0 atom%. As the dopant level increased, the lattice contracted, suggesting the dominant formation of dopant-oxygen vacancy clusters. The smaller than expected lattice contraction can be attributed to the segregation of Zr (one of eleven added dopants) to ABO3 perovskite-type phases that SEM/EDX shows also contain Ba, Ce, and possibly some U. Raman spectroscopy shows that doping leads to a loss of cubic symmetry, possibly associated with tetragonal distortions. Raman mapping confirms this loss of cubic symmetry and suggests the specimen is not uniformly doped. Electrochemical experiments show that these distortions lead to a decrease in the oxidative dissolution rate of the UO2 with increased doping density.Key words: UO2, X-ray diffraction, electrochemistry, Raman spectroscopy, nuclear fission products.

A unique approach to detect chemical speciation and distribution on nanometer-scale nuclear materials has been achieved by the combination of neutron reflectometry and shell-isolated surface-enhanced Raman spectroscopy. Both surface and underlying layers of the uranium oxide materials were determined with angstrom-level resolution. Our results reveal that the UO(x) film is composed of three sublayers: an ∼38 Å thick layer of U(3)O(8) formed along the UO(x)/substrate interface; the adjacent sublayer consists of an ∼900 Å thick single phase of α-UO(3), and the top layer is γ-UO(3) with a thickness of ∼115 Å.