The local structure of Mn-doped Li 2 B 4 O 7 (001) was investigated using extended X-ray absorption fine structure (EXAFS) at the Mn K edge and electron paramagnetic resonance (EPR). The location of the Mn dopant in a lithium tetraborate crystal is consistent with occupation of a site with strong oxygen coordination. The Mn-O bond lengths are similar to those observed with Mn doping of the icosahedral based boron carbide where Mn is in a substitutional dopant in one of the cage sites. From EXAFS, the manganese does not appear to greatly alter the overall tetragonal form of lithium tetraborate, with the dopant most likely substituting for one of the two B sites and with placement of some of the Mn in a Li site still possible. The EPR spectra agree with the literature examined resolving multiple Mn species in the crystal lattice.
The photoelectric work function of nearly stoichiometric (111) and (100) hydrothermally grown UO2 was measured to be 6.28 ± 0.36 eV and 5.80 ± 0.36 eV, respectively. Candidate metals for electrical contacts are identified for both rectifying and non‐rectifying contacts based on work function, lattice compatibility, and electrical conductivity.
The four dopants (Nd, Gd, Dy, and Er) substitutionally occupy the Li + sites in lithium tetraborate (Li 2 B 4 O 7 : RE) glasses as determined by analysis of the extended X-ray absorption fine structure. The dopants are coordinated by 6-8 oxygen at a distance of 2.3 to 2.5 Å, depending on the rare earth. The inverse relationship between the RE-O coordination distance and rare earth (RE) atomic number is consistent with the expected lanthanide atomic radial contraction with increased atomic number. Through analysis of the X-ray absorption near edge structure, the rare earth dopants adopt the RE 3+ valence state. There are indications of strong rare earth 5d hybridization with the trigonal and tetrahedral formations of BO 3 and BO 4 based on the determination of the rare earth substitutional Li + site occupancy from the X-ray absorption near edge structure data. The local oxygen disorder around the RE 3+ luminescence centers evident in the structural determination of the various glasses, and the hybridization of the RE 3+ dopants with the host may contribute to the asymmetry evident in the luminescence emission spectral lines. The luminescence emission spectra are indeed characteristic of the expected f-to-f transitions; however, there is an observed asymmetry in some emission lines.
Arrays of gold-coated nanodomes were fabricated on glass substrates using a soft nanoimprint lithography technique. Optical transmission measurements revealed complex plasmonic resonances that proved highly sensitive to the array dimensions, the thickness of the gold layer, and the refractive index of the surrounding medium. As one promising application for these structures, the refractive index sensing capabilities of the nanodome arrays were assessed.
The electronic properties of ThO 2 single crystals were studied using x-ray photoemission spectroscopy (XPS). The XPS results show that the Th 4f core level is in an oxidation state that is consistent with that expected for Th in ThO 2 . The effective Debye temperature is estimated from the temperature dependent photoemission intensities of the Th 4f core level over the temperature range of 290 to 360 K. A Debye temperature of 468±32 K has been determined.
Single crystals of ThO2, UO2, and their solid solutions, UxTh1–xO2, have been obtained through various hydrothermal growth conditions. This technique offers the better of two other growth processes: (i) single crystal purity as by photochemical growth of nanocrystals; and (ii) large/bulk sizes as obtained by the arc melt method. The band gap of the UxTh1–xO2 single crystal solid solution, along with the luminescence transition, have been characterized. The occupied and unoccupied structures are determined using ultraviolet and inverse photoemission spectroscopy and the electronic band gap was measured to be 3–4 eV. The strain of incorporating U into the ThO2 is analyzed through Vegard's law. In this crystal there are defect and impurity sites, likely arising from the kinetic growth process, giving rise to a similar yet slightly different optical gap evident with cathodoluminescence spectroscopy. There is a major luminescence feature spanning the range from 3.18 to 4.96 eV (250–390 nm) with a maximum at 4.09 eV (303 nm), corresponding with the measured electronic band gap. In this paper, the electronic properties of a solid solution U0.22Th0.78O2 are measured and interpreted compared to the pure actinide oxides, ThO2 and UO2.
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