Quest for Environmentally-Benign Ligands for Actinide Separations: Thermodynamic, Spectroscopic, and Structural Characterization of U(VI) Complexes with Oxa-Diamide and Related Ligands

Complexation of U(VI) with N,N,N{prime},N{prime}-tetramethyl-3-oxa-glutaramide (TMOGA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with their dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including stability constants, enthalpy and entropy of complexation, were determined by spectrophotometry, potentiometry and calorimetry. Single-crystal X-ray diffractometry, EXAFS spectroscopy, FT-IR absorption and laser-induced luminescence spectroscopy were used to obtain structural information on the U(VI) complexes. Like ODA, TMOGA and DMOGA form tridentate U(VI) complexes, with three oxygen atoms (the amide, ether and/or carboxylate oxygen) coordinating to the linear UO{sub 2}{sup 2+} cation via the equatorial plane. The stability constants, enthalpy and entropy of complexation all decrease in the order ODA > DMOGA > TMOGA, showing that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with U(VI) due to the decrease in the entropy of complexation. The trend in the thermodynamic stability of the complexes correlates very well with the structural and spectroscopic data obtained by single crystal XRD, FT-IR and laser-induced luminescence spectroscopy

A laboratory based system for Laue micro x-ray diffraction

A laboratory diffraction system capable of illuminating individual grains in a polycrystalline matrix is described. Using a microfocus x-ray source equipped with a tungsten anode and prefigured monocapillary optic, a micro-x-ray diffraction system with a 10 mum beam was developed. The beam profile generated by the ellipsoidal capillary was determined using the"knife edge" approach. Measurement of the capillary performance, indicated a beam divergence of 14 mrad and a useable energy bandpass from 5.5 to 19 keV. Utilizing the polychromatic nature of the incident x-ray beam and application of the Laue indexing software package X-Ray Micro-Diffraction Analysis Software, the orientation and deviatoric strain of single grains in a polycrystalline material can be studied. To highlight the system potential the grain orientation and strain distribution of individual grains in a polycrystalline magnesium alloy (Mg 0.2 wt percent Nd) was mapped before and after tensile loading. A basal (0002) orientation was identified in the as-rolled annealed alloy; after tensile loading some grains were observed to undergo an orientation change of 30 degrees with respect to (0002). The applied uniaxial load was measured as an increase in the deviatoric tensile strain parallel to the load axis (37 References)

Plastic deformation in Al (Cu) interconnects stressed by electromigration and studied by synchrotron polychromatic X-ray microdiffraction

We report here an in-depth synchrotron radiation based white beam X-ray microdiffraction study of plasticity in individual grains of an Al (Cu) interconnect during the early stage of electromigration. The study shows a rearrangement of the geometrically necessary dislocations (GND) in bamboo typed grains during that stage. We find that about 90percent of the GNDs are oriented so that their line direction is the closest to the current flow direction. In non-bamboo typed grains, the Laue peak positions shift, indicating that the grains rotate. An analysis in terms of force directions has been carried out and is consistent with observed electromigration induced grain rotation and bending

Fabrication and characterization of a new high density Sc/Si multilayer sliced grating

State of the art soft x-ray spectroscopy techniques like Resonant Inelastic X-ray Scattering (RIXS) require diffraction gratings which can provide extremely high spectral resolution of 105-106. This problem may be addressed with a sliced multilayer grating with an ultra-high groove density (up to 50,000 mm-1) proposed in the recent publication [Voronov, D. L., Cambie, R., Feshchenko, R. M., Gullikson, E., Padmore, H. A., Vinogradov, A. V., Yashchuk, V. V., Proc. SPIE 6705, 67050E (2007)]. It has been suggested to fabricate such a grating by deposition of a soft x-ray multilayer on a substrate which is a blazed saw-tooth grating (echellette) with low groove density. Subsequent polishing applied to the coated grating removes part of the coating and forms an oblique-cut multiline structure that is a sliced multilayer grating. The resulting grating has a short-scale periodicity of lines (bilayers), which is defined by the multilayer period and the oblique-cut angle. We fabricated and tested a Sc/Si multilayer sliced grating suitable for EUV applications, which is a first prototype based on the suggested technique. In order to fabricate an echellette substrate, we used anisotropic KOH etching of a Si wafer. The etching regime was optimized to obtain smooth and flat echellette facets. A Sc/Si multilayer was deposited by dc-magnetron sputtering, and after that it was mechanically polished using a number of diamond pastes. The resulting sliced grating prototype with ~;;270 nm line period has demonstrated a dispersive ability in the 41-49 nm photon wavelength range with a diffraction efficiency of ~;;7percent for the optimized 38th order assigned to the echellette grating of 10 mu m period

Alternative Donor--Acceptor Stacks from Crown Ethers and Naphthalene Diimide Derivatives: Rapid, Selective Formation from Solution and Solid State Grinding

Self assembling {pi}-conjugated molecules into ordered structures are of increasing interest in the field of organic electronics. One particular example is charge transfer complexes containing columnar alternative donor-acceptor (ADA) stacks, where neutral and ionic ground states can be readily tuned to modulate electrical, optical, and ferroelectrical properties. Aromatic-aromatic and charge transfer interactions have been the leading driving forces in assisting the self-assembly of ADA stacks. Various folding structures containing ADA stacks were assembled in solution with the aid of solvophobic or ion-binding interactions. Meanwhile, examples of solid ADA stacks, which are more appealing for practical use in devices, were obtained from cocrystalization of binary components or mesophase assembly of liquid crystals in bulk blends. Regardless of these examples, faster and more controllable approaches towards precise supramolecular order in the solid state are still highly desirable

Performance of the upgraded LTP-II at the ALS Optical Metrology Laboratory

The next generation of synchrotrons and free electron laser facilities requires x-ray optical systems with extremely high performance, generally of diffraction limited quality. Fabrication and use of such optics requires adequate, highly accurate metrology and dedicated instrumentation. Previously, we suggested ways to improve the performance of the Long Trace Profiler (LTP), a slope measuring instrument widely used to characterize x-ray optics at long spatial wavelengths. The main way is use of a CCD detector and corresponding technique for calibration of photo-response non-uniformity [J. L. Kirschman, et al., Proceedings of SPIE 6704, 67040J (2007)]. The present work focuses on the performance and characteristics of the upgraded LTP-II at the ALS Optical Metrology Laboratory. This includes a review of the overall aspects of the design, control system, the movement and measurement regimes for the stage, and analysis of the performance by a slope measurement of a highly curved super-quality substrate with less than 0.3 microradian (rms)slope variation

Electromigration-induced plasticity and texture in Cu interconnects

Plastic deformation has been observed in damascene Cu interconnect test structures during an in-situ electromigration experiment and before the onset of visible microstructural damage (ie. voiding) using a synchrotron technique of white beam X-ray microdiffraction. We show here that the extent of this electromigration-induced plasticity is dependent on the texture of the Cu grains in the line. In lines with strong <111> textures, the extent of plastic deformation is found to be relatively large compared to our plasticity results in the previous study [1] using another set of Cu lines with weaker textures. This is consistent with our earlier observation that the occurrence of plastic deformation in a given grain can be strongly correlated with the availability of a <112> direction of the crystal in the proximity of the direction of the electron flow in the line (within an angle of 10{sup o}). In <111> out-of-plane oriented grains in a damascene interconnect scheme, the crystal plane facing the sidewall tends to be a {l_brace}110{r_brace} plane,[2-4] so as to minimize interfacial energy. Therefore, it is deterministic rather than probabilistic that the <111> grains will have a <112> direction nearly parallel to the direction of electron flow. Thus, strong <111> textures lead to more plasticity, as we observe

A velocity map imaging spectrometer for electron?ion and ion?ion coincidence experiments with synchrotron radiation

We have built a velocity imaging (VMI) spectrometer optimized for angle-resolved photoionization experiments with synchrotron radiation (SR) in the VUV and soft X-tay range. The spectrometer is equiped with four electrostatic lenses that focus the charged photoionization products onto a position-sensitive multi-hit delay-line anode. The use of two additional electrostatic lens elements as compared to the standard design of Eppink and Parker [T.J.B. Eppink and D.H. Parker, Rev. Sci. Instrum. 68 (1997) 3477]provides better focusing of an extended interaction region, which is crucial for most SR applications. Furthermore, the apparatus is equipped with a second micro-channel plate detector opposite to the VMI spectrometer, enabling electron-ion coincidence experiments and thereby mass-resolved ion spectroscopy independent of the time structure of the synchrotron radiation. First results for the photofragmentation of CO2 molecules are presented