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

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

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li–S) batteries lead to the formation of solid-electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and other electrolyte components are still unclear. We report an in situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li–S batteries. A multimodal approach involving AIMD modeling and in situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li₂S, LiF, Li₂O, etc.) and formation of a secondary matrix type phase due to cross interaction between reaction products and electrolyte components, which is followed by a highly dynamic monoanionic polysulfide (i.e., LiS₅) fouling process. These new molecular-level insights into the SEI layer evolution on Li-anodes are crucial for delineating effective strategies for the development of Li–S batteries