The work functions of nanocrystalline anatase (TiO2) thin films and a rutile single crystal were measured using photoemission spectroscopy (PES). The nanocrystalline titanium dioxide films were deposited in-vacuum using electrospray thin film deposition. A comparison between ultraviolet photoemission spectroscopy (UPS) and low intensity x-ray photoemission spectroscopy (LIXPS) work function measurements on these samples revealed a strong, immediate, and permanent work function reduction (>0.5 eV) caused by the UPS measurements. Furthermore, it was found that regular XPS measurements also reduce the work function after exposure times ranging from seconds to minutes. These effects are similar in magnitude to artifacts seen previously on indium tin oxide (ITO) substrates characterized with XPS and UPS, and are likely related to the formation of a surface dipole through the photochemical hydroxylation of oxygen vacancies present on the TiO2 surface.
The relationship between the oxidation potential determined by electrochemical measurements and the ionization energies measured by gas-phase ultraviolet photoelectron spectroscopy (UPS) has long been a focus of research of various groups. The focus of this study is to reveal such a correlation for redox molecules, which are chemically attached to metal electrodes. X-ray photoelectron spectroscopy, UPS, and cyclic voltammetry were performed for three types of ferrocene-terminated self-assembled monolayers possessing different electron-donating abilities. The results of these experiments indicate a linear relation with a slope of ∼0.7 between the UPS-derived energy of the highest occupied molecular orbital (HOMO) and the electrochemical oxidation potential. This indicates that the HOMO energy can be used to determine the oxidation potential of chemically modified electrodes.
The work function of nano-crystalline zinc oxide (ZnO) thin films was examined using photoemission spectroscopy (PES). Colloidally dispersed ZnO nano-particles were electrospray-deposited in vacuum to form nano-crystalline thin films. The samples showed an immediate work function reduction by 0.35 eV during ultraviolet photoemission spectroscopy (UPS) measurements. This artifact was detected and quantified through low intensity x-ray photoemission spectroscopy (LIXPS) measurements, which use a very low photon flux. This prevented significant photochemical changes on the measured surface, i.e. the true work function unaffected by the UPS artifact can be measured. Annealing of an identical sample removed all ambient contamination from the ZnO surface with the effect to prevent the work function lowering artifact. This allowed the conclusion that ambient contamination is essential for the artifact to occur, similar to what was observed earlier on indium tin oxide and TiO2 surfaces. In an additional experiment, exposure of the annealed sample to the ambient resulted in a sample that again showed the artifact further demonstrating the necessity of water to be present. This experiment also demonstrated that the solubility enhancing surfactant shell of the nano-crystals does not play a significant role in the artifact, since it was removed during the annealing process.
Bulk niobium Superconducting Radio-Frequency cavities are a leading accelerator technology. Their performance is limited by the cavity loss and maximum acceleration gradient, which are negatively affected by vortex penetration into the superconductor when the peak magnetic field at the cavity wall surface exceeds the vortex penetration field (Hvp). It has been proposed that coating the inner wall of an SRF cavity with superconducting thin films increases Hvp. In this work, we utilized Nb ellipsoid to simulate an inverse SRF cavity and investigate the effect of coating it with magnesium diboride layer on the vortex penetration field. A significant enhancement of Hvp was observed. At 2.8 K, Hvp increased from 2100 Oe for an uncoated Nb ellipsoid to 2700 Oe for a Nb ellipsoid coated with ~200 nm thick MgB2 thin film. This finding creates a new route towards achieving higher acceleration gradient in SRF cavity accelerator beyond the theoretical limit of bulk Nb.
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