Ambient-Pressure X-ray Photoelectron Spectroscopy

This workshop focused on the application of ambient pressure X-ray photoelectron spectroscopy (APXPS) to environmental science and catalysis. Pioneering work on APXPS was done in the early 1970's by Hans and Kai Siegbahn et al., who demonstrated that XPS can operate at pressures of up to 1 Torr. A new type of APXPS instrument that utilizes a differentially-pumped electrostatic lens system at the ALS in 2001 increased the pressure limit to above 5 Torr, which opened the door to XPS experiments on water and aqueous solutions at temperatures above the melting point, in equilibrium with the vapor pressure of water. The impact of APXPS on fields such as environmental and atmospheric science as well as heterogeneous catalysis is already visible in numerous high impact publications. Today several other synchrotron facilities around the world have already implemented beam lines for APXPS or planning to do so in the near future. The goal of this workshop (organized by Miquel Salmeron (Molecular Foundry, LBNL), B. Simon Mun (Advanced Light Source, LBNL) and Hendrik Bluhm (Chemical Sciences Division, LBNL)) was to bring together researchers interested in the technique, review its current progress, discuss scientific opportunities and desirable technical improvements as well as consider the consequences of the increased user demand on the existing beam lines and ways to expand the availability of time

A photoemission study of Pd ultrathin films on Pt (111)

The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer

Understanding the Role of Electronic Effects in CO on the Pt-Sn Alloy Surface via Band Structure Measurements

Using angle-resolved photoemission spectroscopy, we show direct evidence for charge transfer between adsorbed molecules and metal substrates, i.e., chemisorption of CO on Pt(111) and Pt-Sn/Pt(111) 2 x 2 surfaces. The observed band structures show a unique signature of charge transfer as CO atoms are adsorbed, revealing the roles of specific orbital characters participating in the chemisorption process. As the coverage of CO increases, the degree of charge transfer between CO and Pt shows a clear difference to that of Pt-Sn. With comparison to density functional theory calculation results, the observed distinct features in the band structure are interpreted as back-donation bonding states formed between the Pt molecular orbital and the 2 pi orbital of CO. Furthermore, the change in the surface charge concentration, measured from the Fermi surface area, shows that the Pt surface has a larger charge concentration change than the Pt-Sn surface upon CO adsorption. The differences between Pt and Pt-Sn surfaces are due to the effect of Pt-Sn intermetallic bonding on the interaction of CO with the surface

A photoemission study of Pd ultrathin films on Pt(111)

The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer

Controlling the Temperature and Speed of the Phase Transition of VO2 Microcrystals.

We investigated the control of two important parameters of vanadium dioxide (VO2) microcrystals, the phase transition temperature and speed, by varying microcrystal width. By using the reflectivity change between insulating and metallic phases, phase transition temperature is measured by optical microscopy. As the width of square cylinder-shaped microcrystals decreases from ∼70 to ∼1 μm, the phase transition temperature (67 °C for bulk) varied as much as 26.1 °C (19.7 °C) during heating (cooling). In addition, the propagation speed of phase boundary in the microcrystal, i.e., phase transition speed, is monitored at the onset of phase transition by using the high-speed resistance measurement. The phase transition speed increases from 4.6 × 10(2) to 1.7 × 10(4) μm/s as the width decreases from ∼50 to ∼2 μm. While the statistical description for a heterogeneous nucleation process explains the size dependence on phase transition temperature of VO2, the increase of effective thermal exchange process is responsible for the enhancement of phase transition speed of small VO2 microcrystals. Our findings not only enhance the understanding of VO2 intrinsic properties but also contribute to the development of innovative electronic devices

Controlling the Temperature and Speed of the Phase Transition of VO2 Microcrystals.

We investigated the control of two important parameters of vanadium dioxide (VO2) microcrystals, the phase transition temperature and speed, by varying microcrystal width. By using the reflectivity change between insulating and metallic phases, phase transition temperature is measured by optical microscopy. As the width of square cylinder-shaped microcrystals decreases from ∼70 to ∼1 μm, the phase transition temperature (67 °C for bulk) varied as much as 26.1 °C (19.7 °C) during heating (cooling). In addition, the propagation speed of phase boundary in the microcrystal, i.e., phase transition speed, is monitored at the onset of phase transition by using the high-speed resistance measurement. The phase transition speed increases from 4.6 × 10(2) to 1.7 × 10(4) μm/s as the width decreases from ∼50 to ∼2 μm. While the statistical description for a heterogeneous nucleation process explains the size dependence on phase transition temperature of VO2, the increase of effective thermal exchange process is responsible for the enhancement of phase transition speed of small VO2 microcrystals. Our findings not only enhance the understanding of VO2 intrinsic properties but also contribute to the development of innovative electronic devices

Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites

We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3-d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from 80 to 40 kJ mol-1 at a threshold temperature of ca. 320 oC. In situ XPS near-ambient pressure ( 0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 oC. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 oC

In-Situ Nanotribological Properties of Ultrananocrystalline Diamond Films Investigated with Ambient Pressure Atomic Force Microscopy

© 2021 American Chemical Society.The relationship between nanoscale friction and the surrounding environment has long been a critical issue in the field of nanotribology. Here, we utilized ambient pressure-atomic force microscopy to investigate the effect of environmental gas on nanoscale friction of ultrananocrystalline diamond (UNCD) films. The frictional forces were measured in an atomic force microscopy (AFM) chamber in the environmental range from an ultrahigh vacuum to near ambient pressure in the presence of oxygen, nitrogen, and water. We observed that friction increased with the pressure of the oxygen responsible for the oxidation of the surface of the UNCD, while that in nitrogen gas remained unchanged. Interestingly, friction decreased in water, due to the tribochemical reaction caused by surface passivation. When two diamond materials come into contact under water conditions, the water molecules are dissociated because of normal pressure between the AFM tip and diamond surface, and the dissociative water molecule adsorption passivates the surfaces of the diamond-coated tip and UNCD, resulting in a reduction of friction force. The chemical state of the UNCD surface in various environmental conditions was confirmed using near ambient pressure X-ray photoelectron spectroscopy. This result elucidates the role of vapor-phase oxygen and water in the tribological properties of carbon-based materials.11Nsciescopu