Influence of growth rate on the epitaxial orientation and crystalline quality of CeO2 thin films grown on Al2O3(0001)

Growth rate-induced epitaxial orientations and crystalline quality of CeO2 thin films grown on Al2O3(0001) by oxygen plasma-assisted molecular beam epitaxy were studied using in situ and ex situ characterization techniques. CeO2 grows as three-dimensional (3D) islands and two-dimensional layers at growth rates of 1-7 angstrom/min and \u3e = 9 angstrom/min, respectively. The formation of epitaxial CeO2(100) and CeO2(111) thin films occurs at growth rates of 1 angstrom/min and \u3e = 9 angstrom/min, respectively. Glancing-incidence x-ray diffraction measurements have shown that the films grown at intermediate growth rates (2-7 angstrom/min) consist of polycrystalline CeO2 along with CeO2(100). The thin film grown at 1 angstrom/min exhibits six in-plane domains, characteristic of well-aligned CeO2(100) crystallites. The content of the poorly aligned CeO2(100) crystallites increases with increasing growth rate from 2 to 7 angstrom/min, and three out of six in-plane domains gradually decrease and eventually disappear, as confirmed by XRD pole figures. At growth rates \u3e = 9 angstrom/min, CeO2(111) film with single in-plane domain was identified. The formation of CeO2(100) 3D islands at growth rates of 1-7 angstrom/min is a kinetically driven process unlike at growth rates \u3e = 9 angstrom/min which result in an energetically and thermodynamically more stable CeO2(111) surface

In situ formation of 1D nanostructures from ceria nanoparticle dispersions by liquid cell TEM irradiation

Deliberate electron irradiation of cerium oxide nanoparticles in water is used to trigger chemical reactions in a liquid cell transmission electron microscope. Formation of nanorods and nanoneedles is observed starting from predominantly octahedral shape nanoparticles. Detailed morphologies found include free-standing needles, needles connected to specific octahedral ceria facets and star-shaped multi-needle patterns. It is found that rod-axis orientations and crystallographic directions are aligned. It is suggested that high ion and radical concentration of radiolysed water dissolves layers of the original CeO2 particles which re-arrange as needles in the direction of energetically preferred facets

Aqueous Medium Induced Optical Transitions In Cerium Oxide Nanoparticles

Experimental and theoretical investigations were performed to investigate the effect of water on optical properties of nanoceria as a function of Ce3+ concentration. Theoretical studies based on density functional plane-wave calculations reveal that the indirect optical transitions in bare ceria nanoparticles are red-shifted with an increase in the concentration of Ce3+. However, ceria nanoparticles model with adsorbed water molecules show a blue shift in the indirect optical spectra under identical conditions. Direct optical transitions are almost independent of Ce3+ concentration but show a pronounced blue shift in the aqueous environment relative to the bare nanoparticles. The theoretical study is consistent with our experimental observation in difference of shift behaviour in bare and aqueous suspended ceria nanoparticles. This change from red- to blue-shift in indirect optical transitions is associated with the polarization effect of water molecules on f-electron states. This journal i

Surface science analysis of GaAs photocathodes following sustained electron beam delivery

Degradation of the photocathode materials employed in photoinjectors represents a challenge for sustained operation of nuclear physics accelerators and high power free electron lasers (FEL). Photocathode quantum efficiency degradation is due to residual gases in the electron source vacuum system being ionized and accelerated back to the photocathode. These investigations are a first attempt to characterize the nature of the photocathode degradation, and employ multiple surface and bulk analysis techniques to investigate damage mechanisms including sputtering of the Cs-oxidant surface monolayer, other surface chemistry effects, and ion implantation. Surface and bulk analysis studies were conducted on two GaAs photocathodes, which were removed from the JLab FEL DC photoemission gun after delivering electron beam, and two control samples. The analysis techniques include helium ion microscopy, Rutherford backscattering spectrometry (RBS), atomic force microscopy, and secondary ion mass spectrometry (SIMS). In addition, two high-polarization strained superlattice GaAs photocathode samples, one removed from the continuous electron beam accelerator facility (CEBAF) photoinjector and one unused, were also analyzed using transmission electron microscopy (TEM) and SIMS. It was found that heat cleaning the FEL GaAs wafer introduces surface roughness, which seems to be reduced by prolonged use. The bulk GaAs samples retained a fairly well organized crystalline structure after delivering beam but show evidence of Cs depletion on the surface. Within the precision of the SIMS and RBS measurements, the data showed no indication of hydrogen implantation or lattice damage from ion back bombardment in the bulk GaAs wafers. In contrast, SIMS and TEM measurements of the strained superlattice photocathode show clear crystal damage in the wafer from ion back bombardment

Symmetry-Driven Spontaneous Self-Assembly of Nanoscale Ceria Building Blocks to Fractal Superoctahedra

A combination of long-term aging studies and molecular dynamics (MD) simulations has been successfully used to explain the time-dependent hierarchical assembly of ceria nanoparticles (CNPs). When the CNPs were aged in as-synthesized condition at room temperature in water, it was observed that the individual 3−5 nm CNPs result in octahedral superstructures through a fractal assembly. This hierarchical fractal self-assembly was observed despite the absence of any surfactant, at room temperature, and under atmospheric pressure. High resolution transmission electron microscopy (HRTEM) and fast Fourier transform (FFT) analysis have been used to explore the assembly of the individual nanoparticles into fractal superoctahedra. Both experimental work and theoretical analysis showed that the initial octahedral and truncated octahedral seeds symmetrically assemble and result in the superoctahedra with intermediate transformation ste

Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process

Comparison of Superior-Level Facet Joint Violations During Open and Percutaneous Pedicle Screw Placement

BackgroundSuperior-level facet joint violation by pedicle screws may result in increased stress to the level above the instrumentation and may contribute to adjacent segment disease. Previous studies have evaluated facet joint violations in open or percutaneous screw cases, but there are no reports describing a direct institutional comparison.ObjectiveTo compare the incidence of superior-level facet violation for open vs percutaneous pedicle screws and to evaluate patient and surgical factors that affect this outcome.MethodsWe reviewed 279 consecutive patients who underwent an index instrumented lumbar fusion from 2007 to 2011 for degenerative spine disease with stenosis with or without spondylolisthesis. We used a computed tomography grading system that represents progressively increasing grades of facet joint violation. Patient and surgical factors were evaluated to determine their impact on facet violation.ResultsOur cohort consisted of 126 open and 153 percutaneous cases. Percutaneous procedures had a higher overall violation grade (P = .02) and a greater incidence of high-grade violations (P = .006) compared with open procedures. Bivariate analysis showed significantly greater violations in percutaneous cases for age < 65 years, obesity, pedicle screws at L4, and 1- and 2-level surgeries. Multivariate analysis showed the percutaneous approach and depth of the spine to be independent risk factors for high-grade violations.ConclusionThis study demonstrates greater facet violations for percutaneously placed pedicle screws compared with open screws