Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

A study of the interaction between perylene and the TiO2(1 1 0)-(1 × 1) surface-based on XPS, UPS and NEXAFS measurements

The interaction between a semi-large aromatic hydrocarbon compound (perylene) and the TiO₂(1 1 0)-(1 × 1) surface under ultra high vacuum conditions has been probed by X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) and near-edge X-ray absorption fine structure (NEXAFS) methods. UPS measurements of the adsorbate system have been compared with an experimental UPS spectrum of perylene in the gas phase and a calculated spectrum obtained by means of density functional theory (DFT) methods. NEXAFS results of perylene molecules adsorbed on TiO₂(1 1 0)-(1 × 1) were compared with data from an α-phase perylene single crystal. A novel analysis of the valence data has been employed to show that no strong chemical interaction takes place between perylene and the TiO₂(1 1 0)-(1 × 1) surface. Furthermore, angle-dependent NEXAFS measurements and the growth curve results suggest that the perylene molecules are oriented flat down onto the TiO₂ substrate due to weak van der Waals interactions.     

The adsorption and stability of sulfur containing amino acids on Cu{5 3 1}

The adsorption of l-cysteine and l-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K l-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point ‘quadrangular footprint’, whereas l-methionine adsorbs through only two oxygen and a nitrogen atom in a ‘triangular footprint’. NEXAFS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets of the Cu{5 3 1} surface.     

Geometrical characterization of adenine and guanine on Cu(1 1 0) by NEXAFS, XPS, and DFT calculation

Adsorption of purine DNA bases (guanine and adenine) on Cu(1 1 0) was studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine-structure spectroscopy (NEXAFS), and density-functional theory (DFT) calculation. At coverages near 0.2 monolayers, Angular-resolved NEXAFS analysis revealed that adenine adsorbates lie almost flat and that guanine adsorbates are tilted up on the surface with the purine ring parallel to the atom rows of Cu(1 1 0). Referring to the previous studies on pyrimidine DNA bases [M. Furukawa, H. Fujisawa, S. Katano, H. Ogasawara, Y. Kim, T. Komeda, A. Nilsson, M. Kawai, Surf. Sci. 532-535 (2003) 261], the isomerization of DNA bases on Cu(1 1 0) was found to play an important role in the adsorption geometry. Guanine, thymine and cytosine adsorption have an amine-type nitrogen next to a carbonyl group, which is dehydrogenated into imine nitrogen on Cu(1 1 0). These bases are bonded by the inherent portion of -NH-CO- altered by conversion into enolic form and dehydrogenation. Adenine contains no CO group and is bonded to Cu(1 1 0) by participation of the inherent amine parts, resulting in nearly flatly-lying position.     

Thin PTCDA films on Si(0 0 1): 1. Growth mode

We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.     

Thin PTCDA films on Si(0 0 1): 2. Electronic structure

We have studied the thin film formation and the electronic structure of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA), on clean and on hydrogen-passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), angle-resolved photoelectron spectroscopy (ARPES), near edge X-ray absorption fine structure (NEXAFS) and low energy electron diffraction (LEED). On the H passivated surface the changes in the electronic structure of the substrate and the molecules with increasing film thickness are very small. The molecular orbitals show a dispersive behavior, indicating that the PTCDA layers are ordered. On the reactive clean surface the anhydride groups of the molecule interact with the substrate as indicated by changes in the core level binding energies. This results in a much lower ordering in the film compared to PTCDA on a passivated silicon surface. There is no sign of decomposition of the molecule because of the more reactive substrate.     

Photoemission, NEXAFS and STM studies of pentacene thin films on Au(1 0 0)

We have investigated the initial stages of the growth of pentacene thin films on the Au(1 0 0) substrate using synchrotron radiation photoelectron spectroscopy (PES), near edge X-ray absorption fine structure (NEXAFS) and scanning tunnelling microscopy (STM). Results indicate a well-ordered structure with the pentacene molecules adopting a predominantly flat orientation with respect to the substrate for coverages of less than three monolayers. NEXAFS and photoemission data indicates the presence of a second molecular orientation for thicker films, with the introduction of a slight tilting away from planar bonding geometry at higher pentacene coverages. STM images of coverages less than three monolayers indicate a well-ordered pentacene structure allowing for the calculation of pentacene unit cell parameters. The pentacene molecular rows adopt a side-by-side bonding arrangement on the surface. For pentacene deposited at room temperature, step edges were observed to act as nucleation centres for film growth. Annealing of the substrate to 373 K was found to remove excess molecules and improve film quality, but did not otherwise change the bonding geometry of the pentacene with respect to the surface.     

The local adsorption geometry and electronic structure of alanine on Cu{1 1 0}

The adsorption of alanine on Cu{1 1 0} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 × 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (≈26° in plane with respect to and ≈45° out of plane) and the C-N bond angle with respect to could be determined for the pseudo-(3 × 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 × 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature.     

Identification of the vanadyl terminated V2O3(0 0 0 1) surface by NEXAFS spectroscopy: A combined theoretical and experimental study

In this work we present results from density functional theory (DFT) cluster studies to determine polarization-dependent near edge X-ray absorption fine structure (NEXAFS) spectra of the vanadyl termination of the V₂O₃(0 0 0 1) surface. The oxygen K edge spectra are calculated for the relaxed surface geometry where geometric parameters are taken from recent periodic DFT work. A detailed analysis of energetic peak positions, relative intensities, and final state orbitals allows a deep understanding of the complex angular dependence of the calculated spectra on the basis of the local binding environment of differently coordinated oxygen species. Further, our theoretical analysis can assign and explain various spectral details in the experimental NEXAFS data, in particular, those related to vanadyl oxygen. This allows us to support the experimentally suggested vanadyl surface termination.     

Configuration of pentacene (C22H14) films on Si(1 0 0)-2 × 1 studied by NEXAFS

Pentacene films on Si(1 0 0)-(2 × 1) surface at 300 K were investigated using near edge X-ray absorption fine structure (NEXAFS) at the carbon K-edge. NEXAFS spectra show that pentacene molecules are chemisorbed on the Si(1 0 0)-(2 × 1) surface for monolayer with flat-laying and predominantly physisorbed on the Si(1 0 0)-(2 × 1) surface for multilayer films with an upright molecular orientation. Absorption angle of pentacene molecules were measured through π^∗ transition. The angles between the double bond and the silicon surface were 35-55°, 65° and 76° at monolayer, 24 and 48 nm pentacene deposited on the Si(1 0 0) surface, respectively. We observed that the intermediate flat-laying phase is favored for monolayer coverage, while the films of molecules standing perpendicular to the Si(1 0 0) surface are favored for multilayer coverage.     

Electronic structure of octane on Cu(1 1 1) and Ni(1 1 1) studied by near edge X-ray absorption fine structure

The electronic structure of an octane film grown on Cu(1 1 1) and Ni(1 1 1) was studied using C K-edge near edge X-ray absorption fine structure (NEXAFS). A pre-peak was observed on the bulk edge onset for the 1 ML thick octane films on the metal substrates. The pre-peak originated from metal induced gap states (MIGS) in the band gap of octane. The intensity of the pre-peak for octane/Ni(1 1 1) was the same as that of octane/Cu(1 1 1), suggesting that there was little difference in the density of unoccupied MIGS between the octane film on Ni(1 1 1) and Cu(1 1 1). We discuss the metal dependence of the density of unoccupied MIGS on the band structure of the metals.     

Adsorption and decomposition of NO on K-deposited Pd(1 1 1)

The adsorption and decomposition of NO on a K-deposited Pd(1 1 1) surface were investigated using X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, and temperature-programmed desorption. For the K-deposited Pd(1 1 1) surface, two different NO adsorption sites were observed in addition to the Pd site. On the clean Pd(1 1 1) surface, the adsorption of NO was purely molecular and reversible, but on the K-deposited surface, the adsorbed NO decomposed at two different temperatures, 530 and 610 K. These results indicate that the NO adsorption and decomposition sites were newly created by the deposition of K onto the Pd(1 1 1) surface.     

The local structure of SO2 and SO3 on Ni(1 1 1)

The normal incidence X-ray standing wave (NIXSW) technique, supported by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS), has been used to determine the local adsorption geometry of SO₂ and SO₃ on Ni(1 1 1). Chemical-state specific NIXSW data for coadsorbed SO₃ and S, formed by the disproportionation of adsorbed SO₂ after heating from 140 K to 270 K, were obtained using S 1s photoemission detection. For adsorbed SO₂ at 140 K the new results confirm those of an earlier study [Jackson et al., Surf. Sci. 389 (1997) 223] that the molecule is located above hollow sites with its molecular plane parallel to the surface and the S and O atoms in off-atop sites; corrections to account for the non-dipole effects in the interpretation of the NIXSW monitored by S 1s and O 1s photoemission, not included in the earlier work, remove the need for any significant adsorption-induced distortion of the SO₂ in this structure. SO₃, not previously investigated, is found to occupy an off-bridge site with the C_3v axis slightly tilted relative to the surface normal and with one O atom in an off-atop site and the other two O atoms roughly between bridge and hollow sites. The O atoms are approximately 0.87 Å closer to the surface than the S atom. This general bonding orientation for SO₃ is similar to that found on Cu(1 1 1) and Cu(1 0 0) both experimentally and theoretically, although the detailed adsorption sites differ.     

Adsorption and reactivity of SO2 on Ir(1 1 1) and Rh(1 1 1)

The adsorption and reactivity of SO₂ on the Ir(1 1 1) and Rh(1 1 1) surfaces were studied by surface science techniques. X-ray photoelectron spectroscopy measurements showed that SO₂ was molecularly adsorbed on both the Ir(1 1 1) surface and the Rh(1 1 1) surface at 200 K. Adsorbed SO₂ on the Ir(1 1 1) surface disproportionated to atomic sulfur and SO₃ at 300 K, whereas adsorbed SO₂ on the Rh(1 1 1) surface dissociated to atomic sulfur and oxygen above 250 K. Only atomic sulfur was present on both surfaces above 500 K, but the formation process and structure of the adsorbed atomic sulfur on Ir(1 1 1) were different from those on Rh(1 1 1). On Ir(1 1 1), atomic sulfur reacted with surface oxygen and was completely removed from the surface, whereas on Rh(1 1 1), sulfur did not react with oxygen.     

The molecular orientation of DNA bases on H-passivated Si(1 1 1) surfaces investigated by means of near edge X-ray absorption fine structure spectroscopy

Layers of the DNA bases adenine, cytosine, and guanine were deposited onto hydrogen passivated Si(1 1 1) surfaces. The average tilt angles of these molecules with respect to the substrate surface were determined by the angular dependence of the Near Edge X-ray Absorption Fine Structure (NEXAFS) of the carbon K-edge. The interpretation of the NEXAFS spectra was assisted by a semi-empirical approach to the calculation of the π^∗-transition region which employs density functional theory calculations and core level photoemission data.     

Olefin metathesis reaction on GaN (0 0 0 1) surfaces

Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.     

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.     

Bond polarization and image-potential screening in adsorbed C6F6 on Cu(1 1 1)

The orientation of hexafluorobenzene (C₆F₆) on the Cu(1 1 1) surface has been determined for different coverages with the help of near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adsorption geometry and the bonding mode of C₆F₆ differ significantly in comparison to its hydrocarbon analog C₆H₆. C₆F₆ is found to adsorb on Cu(1 1 1) with the ring plane parallel to the surface for coverages below 10 ML. Next to the distinct multilayer, bilayer and monolayer phases we also present evidence of sub-monolayer (i.e., 1/2 ML) coverage with different electronic structure. These findings are explained in a phenomenological model based on fluorine’s property as a σ-acceptor and a π-donor and the resulting bond polarization within the molecule, which is stabilized by image-potential screening within the substrate.     

Adsorption of phenylalanine on single crystal rutile TiO2(1 1 0) surface

The adsorption of the aromatic amino acid, phenylalanine on a TiO₂ rutile (1 1 0) single crystal surface has been investigated with photoemission and NEXAFS (near edge X-ray absorption fine structure) spectroscopy. The results indicate initial adsorption via the carboxylate group in a bidentate configuration with the phenyl ring oriented at approximately 25° to the surface normal. The amino group remains as NH₂. Subsequent layers of phenylalanine appear to adsorb as neutral molecules with H-bonding between NH₂ and CO groups.