Surface and core hole effects in X-ray photoelectron spectroscopy

In XPS analysis, two effects, which significantly reduce the measured peak intensity, are usually neglected: the core hole left behind in an XPS process which causes “intrinsic” excitations and excitations as the photoelectron pass through the surface region. We have calculated these effects quantitatively for various energies, geometries, and materials. Instead of considering the two effects separately, we introduce a new parameter, namely the correction parameter for XPS or CP_XPS, which takes into account both effects. We define this CP_XPS as the change in probability for emission of a photoelectron caused by the presence of the surface and the core hole in comparison with the situation where the core hole is neglected and the electron travels the same distance in an infinite medium. The calculations are performed within the dielectric response theory by means of the QUEELS–XPS software determining the energy-differential inelastic electron scattering cross-sections for X-ray photoelectron spectroscopy (XPS) including surface and core hole effects. This study has been carried out for electron energies between 300 eV and 3400 eV, for angles to the surface normal between 0° and 60° and for various materials. We find that the absolute effect is a reduction by 35–45% in peak intensities but that the variation in CP_XPS with material, angle and energy are < ± 10% for emission angle ≤ 60° and photoelectron energy ≤ 1500 eV. This implies that when XPS analysis is done using relative intensities, the combined effect of the surface and of the core hole is typically less than ≈ ± 10% for geometries and energies normally used in XPS. In practice, it is however difficult to determine the bare peak intensity without the intrinsic electrons because the two overlap in energy.     

Partial intensity approach for quantitative analysis of reflection-electron-energy-loss spectra

We have considered a formalism, known as partial intensity approach (PIA), previously developed to quantitatively analyze reflection electron energy loss (REEL) spectra [1,2]. The aim of the approach is, in particular, to recover the single scattering distribution of energy losses and to separate it into bulk and surface contributions, respectively referred to as the differential inverse inelastic mean free path (DIIMFP) and the differential surface excitation parameter (DSEP). As compared to [1] and [2], we have implemented a modified approach, and we have applied it to the specific geometry of the cylindrical mirror analyzer (CMA), used to acquire the REEL spectra shown here. Silicon, a material with well-defined surface and bulk plasmons, is taken as a case study to investigate the approach as a function of electron energy over the energy range typical of REELS, i.e. from 250 eV to 2 keV. Our goal is, on the one hand, to examine possible limits for the applicability of the approach and, on the other hand, to test a basic assumption of the PIA, namely that a unique DIIMFP and a unique DSEP account for REEL spectra, whatever the acquisition conditions (i.e. electron energy or angle of surface crossing) are. We find that a minimum energy exists below which the PIA cannot be applied and that the assumption of REEL spectra accounted for by unique DIIMFP and DSEP is indeed an approximation.     

Adsorption of water monomer and clusters on platinum(111) terrace and related steps and kinks: I. Configurations,energies, and hydrogen bonding

Adsorption and rotation of water monomer, dimer, and trimer on the (111) terrace, (221) and (322) stepped, and (763) and (854) kinked surfaces of platinum were studied by density functional theory calculations using the PW91 approximation to the energy functional. On the (111) terrace, water monomer and the donor molecule of the dimer and trimer adsorb at atop sites. The per-molecule adsorption energies of the monomer, dimer, and trimer are 0.30, 0.45, and 0.48 eV, respectively. Rotation of monomers, dimers, and trimers on the terrace is facile with energy barriers of 0.02 eV or less. Adsorption on steps and kinks is stronger than on the terrace, as evidenced by monomer adsorption energies of 0.46 to 0.55 eV. On the (221) stepped surface the zigzag extended configuration is most stable with a per-molecule adsorption energy of 0.57 eV. On the (322) stepped surface the dimer, two configurations of the trimer, and the zigzag configuration have similar adsorption energies of 0.55 ± 0.02 eV. Hydrogen bonding is strongest in the dimer and trimer adsorbed on the terrace, with respective energies of 0.30 and 0.27 eV, and accounts for their increased adsorption energies relative to the monomer. Hydrogen bonding is weak to moderate for adsorption at steps, with energies of 0.04 to 0.15 eV, as the much stronger water–metal interactions inhibit adsorption geometries favorable to hydrogen bonding. Correlations of hydrogen bond angles and energies with hydrogen bond lengths are presented. On the basis of these DFT/PW91 results, a model for water cluster formation on the Pt(111) surface can be formulated where kink sites nucleate chains along the top of step edges, consistent with the experimental findings of Morgenstern et al., Phys. Rev. Lett., 77 (1996) 703.     

Core hole and surface excitation correction parameter for XPS peak intensities

In XPS analysis, surface excitations and excitations originating from the static core hole created during the photoexcitation process are usually neglected. However, both effects significantly reduce the measured peak intensity. In this paper we have calculated these effects. Instead of considering the two effects separately, we introduce a new parameter, namely the Correction Parameter for XPS (or CP_XPS) defined as the change in probability for emission of a photoelectron caused by the presence of the surface and the core hole in comparison with the situation where the core hole is neglected and the electron travels the same distance in an infinite medium. The CP_XPS calculations are performed within the dielectric response theory by means of the QUEELS-XPS software determining the energy-differential inelastic electron scattering cross-sections for X-ray photoelectron spectroscopy (XPS) including surface and core hole effects. This study has been carried out for electron energies between 300 eV and 3400 eV, for angles to the surface normal between 0° and 60° and for various materials, especially metals, semiconductors and oxides. For geometries and energies normally used in XPS, i.e. for emission angle ≤ 60° and photoelectron energy ≤ 1500 eV, we find that CP_XPS values are significantly larger for oxides, (0.55 ? CP_XPS ? 0.75) than for metals and semiconductors (0.45 ? CP_XPS ? 0.6). We show that this behavior is due to the difference in the wave vector dispersion of the energy loss function. This dispersion has been determined from analysis of REELS and is found to be free electron like (α ? 1) for metals but is substantially smaller (α ≈ 0.02–0.05) for materials with a wide band gap. As a result, the group velocity of the valence electrons is very small for oxides with a large band gap. This leads to a reduction in the screening of the core-hole potential before the photoelectron has left the region of interaction and thereby to an increase in the intrinsic excitations caused by the core hole.     

Synchrotron-radiation photoemission study of the ultrathin Ba/3C–SiC(111) interface

Electronic structure of the Ba/3C–SiC(111) interface has been detailed studied in situ in an ultrahigh vacuum using synchrotron radiation photoemission spectroscopy with photon energies in the range of 100–450 eV. The 3C–SiC(111) samples were grown by a new method of epitaxy of low-defect unstressed nanoscaled silicon carbide films on silicon substrates. Valence band photoemission and both the Si 2p, C 1s core level spectra have been investigated as a function of Ba submonolayer coverage. Under Ba adsorption two induced surface bands are found at binding energies of 2 eV and 6 eV. It is obtained that Ba/3C–SiC(111) interface can be characterized as metallic-like. Modification of both the Si 2p and C 1s surface-related components were ascertained and shown to be provided by redistribution effect of electron density between Ba adatoms and both the Si surface and C interface atoms.     

Spin-asymmetry in elastic scattering of low-energy electrons from ultrathin Au films on W(110)

We present joint experimental and theoretical results on the elastic scattering of spin-polarized electrons from an epitaxial Au film on a W(110) substrate in the energy range from 8 eV to 27 eV. A time-of-flight technique with a position-sensitive detector is applied to measure secondary emission spectra for spin-up and spin-down primary electrons in a specular geometry. The spin-asymmetry of coherently scattered electrons is obtained by selecting the diffraction spot on the detector. Regions of large asymmetries – with a maximum of about ?60 % – are identified for electron energies of about 14 eV. Relativistic multiple-scattering calculations produce spin-orbit-induced asymmetries which are in agreement with their experimental counterparts. They further reveal that large asymmetries are associated with high intensities. This offers the possibility of an efficient new spin polarimeter with a figure of merit of about 1.5 · 10^?2.     

Density functional calculations for Ni adsorption on Al(1 1 0)

The adsorption of 0.25, 0.5 and 1 monolayer (ML) of the transition metal Ni on the metal substrate Al(1 1 0) was studied using first-principles calculations at the level of density functional theory. The metal–metal system was analyzed with the generalized gradient approximation. Four stable atomic configurations were considered, and the optimized geometries and adsorption energies of different Ni adsorption sites on the Al(1 1 0) surface at selected levels of coverage were calculated and compared. The four-fold hollow site was determined to be the most stable adsorption site with adsorption energy of 5.101 eV at 0.25 ML, 3.874 eV at 0.5 ML and 3.665 eV at 1 ML. The adsorption energies of the four sites slightly decreased as the Ni coverage increased. Work function analysis showed that when Ni is adsorbed on the Al(1 1 0) surface, the work function decreased as the coverage increased due to depolarization. The Mulliken population and density of states were calculated to determine the charge distribution of the adsorption site, confirming that a chemisorption interaction exists between the adsorbed Ni atom and Al(1 1 0) surface atoms.     

Graphene on ordered Ni-alloy surfaces formed by metal (Sn,Al) intercalation between graphene/Ni(111)

Deposition and intercalation of Al and Sn on Ni(111) supported graphene is investigated by Auger electron spectroscopy, low energy electron diffraction, and scanning tunneling microscopy. Al intercalates at ~ 200 °C while Sn intercalates at ~ 350 °C, indicating that the intercalation process is element specific. Both Al and Sn alloy with the Ni-substrate at higher annealing temperatures and form ordered alloy surfaces and surface alloys, respectively. Sn forms a (√3 × √3) R30° surface alloy by substituting surface Ni-atoms with Sn and thus the alloy maintains the same good lattice match with graphene as for Ni(111). Both Sn and Al are interacting weakly with graphene and can therefore be used to decouple graphene from the strongly interacting Ni substrate.     

Surface electronic structure of polar NiO(111) films

The surface and electronic structure of polar NiO(111) films with or without facets, prepared on a Mo(110) substrate, were in situ studied using various surface analytical techniques. A new surface state located at 0.8–1.8 eV measured by electron energy loss spectroscopy was observed on faceted NiO(111) films, which is originated from surface Ni vacancies. This surface state is decreased by annealing or deposition of Ni atoms. The experimental results indicate that the charge transfer occurs between surface and bulk of the faceted NiO(111) films. Present work provides a model surface with polarity and facets, which can be used for further investigation on chemical adsorption of atoms or molecules as well as selective reaction.     

Understanding 4-bromostyrene Adsorption on the Si(001)-(1 × 2) surface: A density functional theory study

Adsorption properties of 4-bromostyrene (Br–Sty) on the Si(001)-(1 × 2) surface are investigated by ab initio calculation based on density functional theory (DFT). For the adsorption of Br–Sty molecule on the Si(001)-(1 × 2) surface, we have assumed two possible cases within: (i) binding on the partially H-terminated surface and (ii) binding on the clean surface. For the first case, we have estimated two different binding sides: (i) Bromine-terminated bindings and (ii) Carbon-terminated binding. The adsorption energies of Br-terminated and C-terminated binding were found as 0.36 eV and 3.76 eV, respectively. In the same manner, we have also assumed two possible binding sides for the clean surface: (i) Br-terminated binding and (ii) ring-shaped binding. We have found adsorption energies for Br-terminated and ring-shaped binding as 0.14 eV and 1.10 eV on the clean surface, respectively. Moreover, the nudged elastic band method (NEB) was used to reveal the adsorption pathway of these binding models. These results serve to understand the possibility of the adsorption of Br–Sty molecules onto different kind of silicon surfaces into different reaction conditions.     

F−, Cl−, Li+ and Na+ adsorption on AlN nanotube surface: A DFT study

Adsorption of two anions (F⁻ and Cl⁻) and two cations (Li⁺ and Na⁺) on the surface of aluminum nitride nanotubes (AlNNTs) is investigated by density functional theory. The reactions are site-selective, so that the cations and anions prefer to be adsorbed atop the N and Al atoms of the tube surface, respectively. The adsorption energies of anions (−4.46 eV for F⁻ and −1.12 eV for Cl⁻) are much higher than those of cations (about −0.17 eV for Li⁺ and −0.12 eV for Na⁺) which can be explained using frontier molecular orbital theory. It was found that the adsorption of anions may facilitate the electron emission from the AlNNT surface by reducing the work function due to the charge transfer occurs from the anions to the tube. It has been predicted that in contrast to the cations the adsorption of anions also obviously increases the electrical conductivity of AlNNT.     

Surface structure of In2O3(111) (1 × 1) determined by density functional theory calculations and low energy electron diffraction

The surface structure of In₂O₃(111) has been investigated by dynamical analysis of low energy electron diffraction data, in conjunction with first principles calculations using density functional theory. The experimental data set consisted of eight independent beams whose intensities were measured for incident energies in the range between 25 eV and 250 eV. In fitting the experimental data it was essential to treat the radii of In and O spheres as variable parameters: following this procedure a final Pendry R factor of 0.31 was obtained. The LEED results are compatible with the calculations and both analyses suggest that the surface structure involves only small vertical relaxations in the outermost of the {[O^2?]₁₂^24?[In³⁺]₁₆⁴⁸⁺[O^2?]₁₂^24?} quadrupolar units that define the (111) surface. The ab initio slab calculations also confirm that lateral relaxations not considered in fitting the experimental data are of very minor importance.     

Dynamical XPS measurements for probing photoinduced voltage changes

Photoillumination with 405 nm laser causes shifts in XPS peaks of n-Si(100), and CdS. To distinguish between surface photovoltage (SPV), and charging, dynamical measurements are performed, while sample is subjected to square wave pulses of ± 10.00 V amplitude, and 10^?3–10⁵ Hz frequency. For n-Si, Si2p peaks are twinned at + 10.00 and ?10.00, yielding always 20.00 eV difference. Photoillumination shifts the twinned peaks to higher energies, but the difference is always 20.00 eV. However, for CdS, the measured binding difference of Cd3d peaks exhibits strong frequency dependence due to charging, which indicates that both fast SPV and slow charging effects are operative.     

Second harmonic response of the Si(111)7 × 7 surface

Optical second harmonic generation spectra have been experimentally obtained from a clean Si(111) 7 × 7 in two different polarization configurations isolating the rotational anisotropic and isotropic contributions. The energy of the fundamental photon is varied from 0.8 eV to 2.5 eV. For comparison, we also use a microscopic formulation based on the semi-empirical tight binding method to evaluate the nonlinear surface susceptibility tensor χ(2ω). Good agreement between theory and experiment is obtained with respect to the number of resonances, their position in energy, and surface or bulk character.     

Quantum size effect in low energy electron diffraction of thin films

Low energy electron microscopy (LEEM) is used to study the quantum size effect (QSE) in electron reflectivity from thin films. Strong QSE interference peaks are seen below 20 eV for Cu and Ag films on the W(1 1 0) surface and Sb films on the Mo(0 0 1) surface. Simple inspection of QSE interference peaks reveals that all three metals grow atomic layer-by-atomic layer. Layer-specific I(V) spectra obtained with LEEM permit structural analysis by full dynamical multiple scattering LEED calculations for a layer-by-layer view of thin film structure.     

Manganese doping influence on the plasmon energy of nickel films

Manganese doping in nickel films capped with copper have been prepared by evaporation in vacuum. The films are composed of grains with an average diameter of ~ 20 nm from scanning electron microscope scans. Optical absorption is measured over a wavelength range of 190–450 nm. Two plasmon peaks are observed at 3.30 eV and 4.45 eV for a range of concentrations of films. The 4.45 eV peak is a bulk plasmon peak that is enhanced by increasing the manganese in nickel. The 3.30 eV peak is a surface plasmon peak that increases in width or strength of plasmon resonance with increasing concentration of manganese. This may be a combination effect of charge carrier concentration and dielectric screening from the reformed electronic band structure caused by manganese doping. By adding manganese into nickel, the ferromagnetic order is further destroyed as a transition into a spin glass occurs. This spin glass behavior is seen in a coercivity measurement at 4 K where the coercivity drops precipitously as the doping concentration increases.     

Vibrational spectroscopy of oxygen on the (100) and (111) surfaces of lanthanum hexaboride

Reflection absorption infrared spectroscopy (RAIRS) and high resolution electron energy loss spectroscopy (HREELS) have been used to study the adsorption of oxygen on the (100) and (111) surfaces of lanthanum hexaboride. Exposure of the surface at temperatures of 95 K and above to O₂ produces atomic oxygen on the surface and yields vibrational peaks in good agreement with those observed in previous HREELS studies. On the La-terminated (100) surface, RAIRS peaks correspond to vibrations of the boron lattice that gain intensity due to a decrease in screening of surface dipoles that accompanies oxygen adsorption. A sharp peak at ～ 734 cm^?1 in the HREEL spectrum shows isotopic splitting with RAIRS into two components at 717 and 740 cm^?1 with full widths at half maxima of only 12 cm^?1. The sharpness of this mode is consistent with its interpretation as a surface phonon that is well separated from both the bulk phonons and other surface phonons of LaB₆. On the boron-terminated LaB₆(111) surface, broad and weak features are assigned to both vibrations of the boron lattice and of boron oxide. On the (100) surface, oxygen blocks the adsorption sites for CO, and adsorbed CO prevents the dissociative adsorption of O₂.     

DFT study of self-coupling reaction of CF2(ads) coadsorbed on Cu(111) surface for forming CF2=CF2(g)

Total energy calculations based on the density functional theory (DFT) with ultrasoft pseudopotential, generalized gradient spin-polarized approximation and the partial structural constraint path minimization (PSCPM) method were carried out to establish the energetically more favorable reaction pathways for the self-coupling reaction of coadsorbed CF_2(ads) leading to the formation of CF₂=CF_2(ads) on the Cu(111) surface. In addition, the calculated electronic properties, namely partial density of states (PDOS), suggest that the initial breaking of the Cu(111)–CF_2(ads) bond associating with the electron delocalization on the Cu(111) surface and the electron transfer from Cu(111) to both units of CF_2(ads) are factors controlling the energy barrier for self-coupling reaction. Finally, the calculated energy barrier (0.310 eV) for the self-coupling reaction of CF_2(ads) coadsorbed on the Cu(111) surface in comparison with that (0.204 eV) for the single α-fluoride elimination of adsorbed CF_3(ads) on the Cu(111) surface qualitatively manifests that the formation of CF₂ = CF_2(g) at 250 K is limited by the self-coupling reaction of coadsorbed CF_2(ads) instead of the single α-fluoride elimination of adsorbed CF_3(ads).     

Emission of Cu-related complexes in ZnO:Cu nanocrystals

Photoluminescence (PL), its temperature dependence, scanning electronic microscopy (SEM) and X ray diffraction (XRD) have been applied for the comparative study of varying the emission, morphology and crystal structure of ZnO and ZnO:Cu nanocrystals (NCs) versus technological routines, as well as the dependence of ZnO:Cu NC parameters on the Cu concentration. A set of ZnO and ZnO Cu NCs was prepared by the electrochemical (anodization) method at a permanent voltage and different etching durations with follows thermal annealing at 400 °C for 2 h in ambient air. The size of ZnO NCs decreases from 300 nm×540 nm down to 200 nm×320 nm with etching duration increasing. XRD study has confirmed that thermal annealing stimulates the ZnO oxidation and crystallization with the formation of wurtzite ZnO crystal lattice. XRD method has been used for monitoring the lattice parameters and for confirming the Cu doping of ZnO Cu NCs. In ZnO Cu NCs four defect related PL bands are detected with the PL peaks at 1.95–2.00 eV (A), 2.15-2.23  eV (B), 2.43–2.50 eV (C) and 2.61–2.69 eV (D). Highest PL intensities of orange, yellow and green emissions have been obtained in ZnO Cu NCs with the Cu concentration of 2.28 at%. At Cu concentration increasing (≥2.28 at%) the PL intensities of the bands A, B, C decrease and the new PL band peaked at 2.61–2.69 eV at 10 K appears in the PL spectrum. The variation of PL intensities for all PL bands versus temperature has been studied and the corresponding activation energies of PL thermal decay have been estimated. The type of Cu-related complexes is discussed using the correlation between the PL spectrum transformation and the variation of XRD parameters in ZnO Cu NCs.     

Photoemission spectroscopy at MOVPE-prepared InGaAs(100) surface reconstructions

Angular resolved ultraviolet photoemission spectroscopy at BESSY was employed to study the electronic structure of the three different, (4 × 3)-, (2 × 4)-, and (4 × 2)-surface reconstructions of In_0.53 Ga_0.47As, which was grown lattice-matched to InP(100). The surfaces have been prepared using metal organic vapor phase epitaxy (MOVPE). For spectroscopy, a dedicated transfer system was employed and samples were transferred contamination-free from the MOVPE reactor to UHV-based analysis tools. For the different surface reconstructions, the Γ ? Δ ? X direction was scanned while varying the photon energy between 10 eV and 28 eV. We observed two surface states in the photoelectron spectra on all of these surface reconstructions in addition to the bulk derived valence band emissions. Different binding energies of the surface states originating from different surface band bending were detected and described.