X-ray Free Electron Laser Studies of Electron and Phonon Dynamics of Graphene Adsorbed on Copper

We report optical pumping and X-ray absorption spectroscopy experiments at the PAL free electron laser that directly probe the electron dynamics of a graphene monolayer adsorbed on copper in the femtosecond regime. By analyzing the results with ab-initio theory we infer that the excitation of graphene is dominated by indirect excitation from hot electron-hole pairs created in the copper by the optical laser pulse. However, once the excitation is created in graphene, its decay follows a similar path as in many previous studies of graphene adsorbed on semiconductors, i e. rapid excitation of SCOPS (Strongly Coupled Optical Phonons) and eventual thermalization. It is likely that the lifetime of the hot electron-hole pairs in copper governs the lifetime of the electronic excitation of the graphene.Comment: 22 pages, 8 Figures including Supplementary Materia

Transition metal oxide surfaces : Surface structures and molecular interaction

Metal oxides are both corrosion products and useful materials with a wide range of applications. Two of the most used metals today are iron and copper. In this thesis, surface structures and molecular interaction with surfaces of iron oxides and copper oxides are studied using spectroscopy and microscopy methods.   The surface structures of iron oxides grown on the low-index iron (Fe) surfaces (100) and (110) have been studied during the initial oxidation phase. The oxidation condition for both iron surfaces was 400 °C and 1×10−6 mbar of oxygen gas. For the Fe(100)-surface, a Fe3O4(100)-film is formed beyond the oxygen adsorbate structures. For the Fe(110)-surface, a FeO(111)-film is first formed. When the FeO(111)-film grows thicker, it transforms into a Fe3O4(111)-film.   The surface structures of Cu2O(100) was studied and the main finding is that the most common surface structure that previously in literature has been described to have a periodicity of (3√2×√2)R45° actually has a periodicity described by the matrix (3,0;1,1). Furthermore, the low-binding energy component in the photoelectron spectroscopy O 1s-spectrum is determined to origin from surface oxygen atoms.   Sulfur dioxide, a corrosive molecule that in the environment to large share comes from human activities such as burning of fossil fuels, was studied using photoelectron spectroscopy when interacting with surfaces of iron oxide thin films and bulk Cu2O-surfaces. On the iron oxide thin film surfaces under ultra-high vacuum conditions, sulfur dioxide adsorbs partly as SO4-species and partly dissociates and forms FeS2. On the Cu2O-surfaces under ultra-high vacuum conditions, the adsorption of sulfur dioxide is non-dissociative and forms SO3-species. When interacting with near-ambient pressures of water, it is observed in the photoelectron spectroscopy S 2p-region that the sulfur from SO3-species shifts to Cu2S.QC 20161114</p

Oxidation of Fe(110) in oxygen gas at 400 degrees C

The initial oxidation of Fe(110) in oxygen gas at 400 degrees C beyond initial adsorbate structures has been studied using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, low-energy electron diffraction, and scanning tunneling microscopy (STM). Formation of several ordered phases of surface oxides is observed at oxygen coverages between approximately 2.3 and 3.5 oxygen atoms/Fe(110) surface atom. Initially, a FeO(111)-like film is formed with a parallelogram-shaped moire pattern. It has two mirror domains that are formed symmetrically around the growth direction of a zigzag-shaped adsorbate structure. With increased local oxygen coverage, the moire structure transforms into a ball-shaped form. Both these moire structures have equal atomic stacking at the surface and equal apparent height in STM, suggesting oxygen ions diffusing into the film upon oxidation and that the oxide growth takes place at the iron-iron oxide interface. The FeO(111)-like film turns into a Fe3O4(111)-like film with a triangular bistable surface termination as the oxidation proceeds further. The FeO(111)-like film growth proceeds according to the Frank-van der Merwe mechanism while the Fe3O4(111)-like film grows according to the Stranski-Krastanov mechanism. (C) 2015 Elsevier B.V. All rights reserved

Initial Fe3O4(100) Formation on Fe(100)

The initial oxidation of Fe(100) at 400 degrees C has been studied by X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction, in combination with density functional theory calculations. The first observed well-ordered surface oxide is formed at a coverage of similar to 3 oxygen atoms per unreconstructed surface Fe(100) atom. STM shows that this surface oxide is terminated by straight atomic rows exhibiting a p(2 X 1) periodicity. However, already for oxide films with a coverage of similar to 4 oxygen atoms (corresponding to one Fe3O4 unit cell thickness), wiggly atomic rows appear similar to the c(2 X 2) reconstructed Fe3O4 (100)-surface with the Fe3O4 unit vectors rotated 45 degrees to Fe(100). The wiggly rows are a consequence of subsurface cation iron vacancies, which previously have been observed for bulk surfaces. The formation of subsurface vacancies is supported by the XPS O is signature, which is modeled by considering the core-level shifts for all oxygen atoms in the film. Throughout the oxidation series, the microscopy results reveal a layer-by-layer (Frank-van der Merwe) growth

Scanning tunneling microscopy study of PTCDI on Sn/Si(111)-2√3×2√3

Perylene tetracarboxylic diimide molecules were evaporated onto a Sn/Si(111)-2 root 3 x 2 root 3 surface and studied using scanning tunneling microscopy (STM) and low energy electron diffraction. At low coverages, single molecules are locked into specific adsorption geometries, which are investigated in detail using high resolution STM. The electronic structure of these individual molecules was studied using bias dependent STM images. The molecules form 1D rows that become more common with increasing coverages. Possible intermolecular O center dot center dot center dot H interactions within the rows have been identified. At around half of a monolayer (ML), the rows of molecules interact with each other and form a commensurate 4 root 3 x 2 root 3 reconstruction. In a complete monolayer, several structures emerge as molecules fill in the space between the 4 root 3 x 2 root 3 stripes. Possible intermolecular interactions within the 1 ML structures have been discussed. At coverages above 1 ML, the growth is characterized by island growth, where the molecules are arranged according to the canted structure within the layers.Artikeln tidigare publicerad som manuskript i Emanuelssons (2018) doktorsavhandling Electronic Structure and Film Morphology Studies of PTCDI on Metal/Semiconductor Surfaces </p

Inverse single-site Fe-1(OH)(X)/Pt(111) model catalyst for preferential oxidation of CO in H-2

Inverse oxide/metal model systems are frequently used to investigate catalytic structure-function relationships at an atomic level. By means of a novel atomic layer deposition process, growth of single-site Fe1Ox on a Pt(111) single crystal surface was achieved, as confirmed by scanning tunneling microscopy (STM). The redox properties of the catalyst were characterized by synchrotron radiation based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). After calcination treatment at 373 K in 1 mbar O-2 the chemical state of the catalyst was determined as Fe3+. Reduction in 1 mbar H-2 at 373 K demonstrates a facile reduction to Fe2+ and complete hydroxylation at significantly lower temperatures than what has been reported for iron oxide nanoparticles. At reaction conditions relevant for preferential oxidation of CO in H-2 (PROX), the catalyst exhibits a Fe3+ state (ferric hydroxide) at 298 K while re-oxidation of iron oxide clusters does not occur under the same condition. CO oxidation proceeds on the single-site Fe-1(OH)(3) through a mechanism including the loss of hydroxyl groups in the temperature range of 373 to 473 K, but no reaction is observed on iron oxide clusters. The results highlight the high flexibility of the single iron atom catalyst in switching oxidation states, not observed for iron oxide nanoparticles under similar reaction conditions, which may indicate a higher intrinsic activity of such single interfacial sites than the conventional metal-oxide interfaces. In summary, our findings of the redox properties on inverse single-site iron oxide model catalyst may provide new insights into applied Fe-Pt catalysis

A well-ordered surface oxide on Fe(110)

A well-ordered surface oxide grown on Fe(110) has been studied using scanning tunneling microscopy (STM), low energy electron diffraction, low energy electron microscopy, and core level photoelectron spectroscopy. The iron oxide film exhibits wide terraces and is formed after exposure to 100-1000 L at 1 x 10(-6) mbar O-2 and 400 degrees C. Two domains, mirror symmetric in the Fe(110)-lattice mirror symmetry planes but otherwise equal, are observed. The surface oxide forms a relatively large coincidence surface unit cell (16.1 angstrom x 26.5 angstrom). Imaging by STM reveals a strong bias dependence in the apparent height within the surface unit cell. The oxygen terminating atomic layer has a hexagonal atomic structure, FeO(111)-like, with the atomic sparing of 3.2 angstrom, that is expanded by similar to 63% relative to bulk FeO(111). (C) 2015 Elsevier B.V. All rights reserved

Direct Evidence of Subsurface Oxygen Formation in Oxide-Derived Cu by X-ray Photoelectron Spectroscopy

Subsurface oxygen has been proposed to be crucial in oxide-derived copper (OD-Cu) electrocatalysts for enhancing the binding of CO intermediates during CO$_2$ reduction reaction (CO$_2$RR). However, the presence of such oxygen species under reductive conditions still remains debated. In this work, the existence of subsurface oxygen is validated by grazing incident hard X-ray photoelectron spectroscopy, where OD-Cu was prepared by reduction of Cu oxide with H$_2$ without exposing to air. The results suggest two types of subsurface oxygen embedded between the fully reduced metallic surface and the Cu$_2$O buried beneath: (i) oxygen staying at lattice defects and/or vacancies in the surface-most region and (ii) interstitial oxygen intercalated in metal structure. This study adds convincing support to the presence of subsurface oxygen in OD-Cu, which previously has been suggested to play an important role to mitigate the σ-repulsion of Cu for CO intermediates in CO$_2$RR

Applicability of MOS structures in monitoring catalytic properties, as exemplified for monolayer-iron-oxide-coated porous platinum films

Metal Oxide Semiconductor (MOS) capacitor devices comprised of monolayer iron oxide-coated as well as non-coated polycrystalline Pt deposited on oxidized silicon carbide substrates have been fabricated and their usefulness as realistic model systems in catalyst studies development was evaluated. The CO oxidation characteristics of both iron oxide- and non-coated Pt catalysts were investigated using mass spectrometry, monitoring the carbon dioxide production rate for different combinations of carbon monoxide (CO) and oxygen concentrations at various temperatures. Additionally, the output capacitance of the MOS model catalysts was recorded for each individual CO oxidation activity. A low-temperature shift in CO oxidation characteristics for the monolayer-coated compared to the non-coated Pt catalysts was observed, similar to that previously reported for monolayer iron oxide grown on single-crystalline Pt substrates. A strong correlation between the output capacitance of the MOS structures and the CO oxidation characteristics was found for both monolayer- and non-coated model catalysts. Furthermore, the devices exhibit retained MOS electrical output and CO oxidation characteristics as well as an unaffected catalyst surface composition, as confirmed by photoelectron spectroscopy, even after 200 h of continuous model catalyst operation. In addition to the implications on practical applicability of monolayer iron oxide coating on widely used polycrystalline Pt films in real-world catalysts and sensors, the findings also point to new possibilities regarding the use of MOS model systems for in situ characterization, high throughput screening, and tailoring of e.g. catalyst- and fuel-cell-electrode materials for specific applications. (C) 2016 Elsevier Inc. All rights reserved.Funding Agencies|VINN Excellence Center in research and innovation on Functional Nanoscale Materials (FunMat) by the Swedish Governmental Agency for Innovation Systems (VINNOVA); Swedish Research Council (VR) [2015-04062]; Swedish Foundation for Strategic Research (SSF) through the Future Research Leaders 5 program</p