Analysis of the Auger-photoelectron coincidence spectroscopy (APECS) spectra of metallic Pd,Ag, and Sn

The M45-level photoelectron spectrum of Ag metal measured in coincidence with the M45–VV(¹G) Auger-electron line is analyzed by taking into account the possibility of the M4–M5–VV Coster–Kronig (CK)-transition preceded Auger transition. We denote the atomic shells Mx(Mxy) and Nxy (x, y = 4,5) by MX(MXY) and V, respectively. The M4–M5 CK-transition rate is very small. The M45–VV Auger-electron spectra of metallic Pd and Sn measured in coincidence with the M4 (or M5)-level photoelectron line are analyzed. The M4–M5 CK-transition rates are also very small in metallic Pd and Sn. The coincidence Auger-electron line previously interpreted as the M4–M5–VV (or M4–M5V–VVV) Auger-electron line is largely due to the inelastically scattered M5-level photoelectron background beneath the M4-level photoelectron line. The APECS spectrum of Pd metal shows the first evidence of the M5V–VVV transition of the localized M5V shakeup two-hole state. The intensity ratio of the inelastically scattered Auger-electron background to the M5–VV Auger-electron main line of Ag metal measured in coincidence with the inelastically scattered M5-level photoelectron background beneath the M4-level photoemission line increases, as compared to that measured in coincidence with the M5-level photoelectron main line. This is because when the probability of the photoelectron being inelastically scattered increases, that of the Auger electron emitted by the same ionized atom, being inelastically scattered increases. In other words the photoelectrons and the Auger electrons are originated from the deeper atomic sites (longer pathlength).     

A comparative analysis of electron spectroscopy and first-principles studies on Cu(Pd) adsorption on MgO

Ultrathin MgO films were grown on a W(1 1 0) substrate while metastable impact electron (MIES) and photoelectron (UPS) spectra were measured in situ; apart from the valence band emission, no additional spectral features were detected. The oxide surface was exposed to metal atoms (Cu, Pd) at RT. A comparison with the DOS extracted from first-principles DFT calculations shows that the metal-induced intensity developing above the top of the O 2p valence band in the UP spectra under Cu(Pd) exposure is caused by Cu 3d (Pd 4d) emission. The emission seen in the MIES spectra is attributed to the ionization of Cu 3d and 4s states of adsorbed neutral Cu atoms in an Auger process, Auger neutralization, involving two electrons from the surface, at least one of them from the metal adsorbate. The shape of the MIES spectra suggests metallic island growth even at the lowest studied exposures, which is supported by the first-principles calculations.     

Electron-Spectroscopic Studies of Thermal Stability of Pd/Nb Surfaces

The room-temperature growth of Pd on a clean quasiamorphous, nanostructured Nb surfaces and thermal stability of Pd/Nb interface in the temperature range (295-660) K have been studied by X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy. The measured spectra of Pd (3d) and Nb (3d) electrons indicate presence of a surface Pd-Nb alloy-like phase in the region of submonolayer Pd coverage at room temperature. The Pd (3d) core level shifts can be explained in terms of initial state effects. For multilayer deposits an intermetallic phase is observed in the Pd/Nb interface at room temperature. Inward diffusion of Pd occurs folowed by the formation of three-dimensional alloy at temperatures above 500 K.     

Adsorption of hydrogen and deuterium on potassium-promoted Pd(100) surfaces

The adsorption of H₂ and D₂ has been studied on clean and K-promoted Pd(100) surfaces using thermal desorption, work function changes, ultraviolet photoelectron and Auger spectroscopy. The potassium adlayer significantly lowers the sticking coefficient (from 0.6 to 0.06 at θ_k = 0.2), and the uptake of hydrogen, but increases the desorption energy for H₂ desorption. Calculation showed that each potassium adatom blocks approximately 4–5 adsorption sites for H₂ adsorption. Atomization of hydrogen led to an increase of hydrogen uptake. The adsorption of potassium on the H-covered surface caused a significant decrease in the amount of hydrogen adsorbed on the surface (as indicated by less desorbing hydrogen below 500 K) and promoted the dissolution of H atoms into the bulk of Pd. The dissolved hydrogen was released only above 600–650 K. In the interpetation of the results the extended charge transfer from K-dosed Pd to the adsorbed H atoms and the direct interaction between adsorbed H and K adatoms are taken into account.     

Formation and characterization of Au/Pd surface alloys on Pd(1 1 1)

The formation of alloys by adsorbing gold on a Pd(1 1 1) single crystal substrate and subsequently annealing to various temperatures is studied in an ultrahigh vacuum by means of Auger and X-ray photoelectron spectroscopy. The nature of the alloy surface is probed by CO chemisorption using temperature-programmed desorption and reflection-absorption infrared spectroscopy. It is found that gold grows in a layer-by-layer fashion on Pd(1 1 1) at 300 K, and starts to diffuse into the bulk after annealing to above ∼600 K. Alloy formation results in a ∼0.5 eV binding energy decrease of the Au 4f XPS signals and a binding energy increase of the Pd 3d features of ∼0.8 eV, consistent with results obtained for the bulk alloy. The experimentally measured CO desorption activation energies and vibrational frequencies do not correlate well with the surface sites expected from the bulk alloy composition but are more consistent with significant preferential segregation of gold to the alloy surface.     

Surface composition of PdAu and PdAg catalysts by auger electron spectroscopy

Auger electron spectroscopy (AES) has been employed to examine the metal surface composition of PdAu and PdAg alloys as microspheres and as alumina-supported crystallites. For the PdAu system the observed PdAu ratios at the surface correspond closely to those of the bulk both for the microspheres and crystallites. However in the case of supported PdAg, the surface exhibits silver-enrichment relative to the bulk. By means of the regular solution monolayer model the results are interpreted theoretically and the binding energies between the dissimilar metal atoms are computed.     

Effects of potassium on the adsorption and dissociation of CH3Cl on Pd(100)

The effects of potassium on the adsorption and dissociation of CH₃Cl on a Pd(100) surface has been investigated by ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), electron energy loss spectroscopy (in the electronic range EELS), temperature-programmed desorption (TPD) and work function change. In contrast to the clean surface, the adsorption of CH₃Cl caused a significant work function increase, 0.9-1.4 eV, of potassium-dosed Pd. Preadsorbed K enhanced the binding energy of CH₃C1 to the surface and induced the dissociation of adsorbed molecules. The extent of the dissociation increased almost linearly with the potassium content. The appearance of a new emission in the UPS spectrum at 9.2 eV, attributed to adsorbed CH₃ species, and the low-temperature formation of ethane suggest that a fraction of adsorbed CH₃Cl dissociates even at 115–125 K on potassium-dosed Pd(100). At the same time, a significant part of adsorbed CH₃ radical is stabilized, the reaction of which occurs only at 250–300 K. By means of TPD measurements, H₂, CH₄, C₂H₆, C₂H₄, KCl and K were detected in the desorbing gases. The results are interpreted by assuming a through-metal electronic interaction at low potassium coverage and by a direct interaction of the Cl in the adsorbed CH₃Cl with potassium at high potassium coverage. The latter proposal is supported by the electron excited Auger fine structure of the Cl signal and by the formation of KCl in the desorbing gases.     

Surface segregation in a Ni-1 at% Pd alloy

The surface composition of a Ni-1 at% Pd alloy has been determined by Auger electron spectroscopy after equilibration of the alloy at several temperatures in the range 550 to 800°C. Moderate segregation of Pd to the surface of the alloy has been observed, with concentrations of up to ~～30 at% being detected at the surface after equilibration at 550°C. The heat of segregation (or adsorption) of Pd has been found to agree reasonably well with the predictions of a previously developed unified model of surface segregation in alloys. The kinetics of Pd segregation to the surface have also been measured between 500 and 700°C. Analysis of the kinetic data yields apparent diffusivities of Pd through the alloy that are suggestive of a dominant grain boundary transport mechanism.     

Adsorbed state and vibrational excitation of N2 on Pd(110)

High-resolution vibrational electron energy loss spectroscopy, low-energy electron diffraction and Auger electron spectroscopy have been used to study the interactions of nitrogen with the Pd(110) surface. At 120 K, N₂ is chemisorbed molecularly on the Pd(110) surface, and the (2 × 1)-N₂ structure is formed. Most probably, the N₂ molecules are chemisorbed in the on-top sites of the bulk-like Pd(110) surface in the upright-linear structure. The Pd---N₂ bond energy is estimated to be ˜ 6 kcal/mol. The Pd---N₂ and N---N stretching vibrations of N₂ admolecules on Pd(110) are observed at 30 and 278 meV, respectively. The primary-energy dependence and angle dependence of their excitation cross sections agree reasonably well with the prediction of the dipole theory. The electron beam-induced effects are briefly discussed.     

The temperature dependence of the interaction of oxygen with Pd(111); A study by photoemission and auger spectroscopy

The temperature dependence of the different binding states of oxygen on Pd(111) has been studied using photoemission spectroscopy and Auger spectroscopy. By examining the oxygen 2s binding energies, three distinct states are observed, which are identified as surface chemisorbed oxygen, oxygen incorporated into the first Pd layer, and subsurface oxygen. Changes in the relative oxygen Auger peak heights for 1000 K exposure temperature are explained if the oxygen is assumed to become more negatively charged as it penetrates the Pd surface. A model for the interaction of oxygen with the Pd(111) surface is proposed.     

Auger energy shifts in fcc AgPd random alloys from complete screening picture and experiment

We extend the complete screening picture to ab initio calculations of Auger kinetic energy and Auger parameter shifts in metallic alloys. Experimental measurements of the L(3)M(4,5)M(4,5) Auger transition in fcc AgPd random alloys are compared with first-principles calculations and the results are in excellent agreement for both the Ag and Pd Auger shifts over the whole concentration range. We discuss the Auger kinetic energy shifts in terms of single-hole states for the 2p(3/2) core level and double-hole states for the 3d(5/2) level.     

Electron excited Auger line shape study of ion-beam-mixed Pd–Au alloys

The electronic structure of the ion-beam-mixed Pd–Au alloys have been studied using valence band spectra of XPS and electron excited CVV–Auger spectra. To show the relationship between the electronic structure changes and the Auger spectral line shape, the data of the self-convolution of the partially weighted valence band spectra was compared with the Auger spectra of Pd–Au alloys. The Pd–Au alloy is one of the systems which both atomic and band-like contributions are evident in the Auger spectral line shape. Since the self-convolution of PDOS’s relates to the band-like part of Auger spectra, in Pd–Au alloys, the band-like structure in the Auger line shape can be classified by the self-convolution of the partially weighted valence band spectra. Finally, we found that the increase in peak size at ∼80 eV with the increase in Pd content is due to the band-like contribution in the Au N_6,7VV Auger line shape.     

X-ray photoelectron (XPS) and Auger (XAES) spectroscopy study of rhodium dispersed on carbon substrate

Photoelectron 3d_5/2 binding and Auger M₅VV kinetic energies of dispersed rhodium have been measured. For the smallest deposition of Rh the shifts 0·6 eV and -2·5 eV of 3d_5/2 and M₅VV lines respectively have been found. Electron core level energy, Auger kinetic energy and Fermi edge shifts have been interpreted by a model based on electrostatic relaxation mechanism in metal particles and initial state contribution of surface atoms. Intensity and background height analysis indicate only surface distribution of Rh.I wish to express my gratitude to Dr. Zdenk Bastl for helpful discussions.     

Segregation at the surface of an Au/Pd alloy exposed to CO

We use density functional theory (DFT) with the generalized gradient approximation (GGA) and the revised Perdew-Burke-Ernzerhoff (rPBE) functional, to study the surface composition of the (1 1 1) and (1 0 0) dilute Pd/Au alloy. We find that the energy of Pd atoms is lower when they substitute an Au atom in the bulk than when they substitute an Au atom in the surface layer, or when they are adsorbed on the surface. Whether they are in the surface layer or in the bulk, the Pd atoms interact very weakly with each other. CO adsorbs on the Pd atom in the surface layer and the energy of this complex is lower than that of CO in gas and Pd atom in the bulk. The interaction between the PdCO complexes formed when CO adsorbs on a Pd atom imbedded in the surface layer, is also negligible. We use these energies, equilibrium thermodynamics, and a simple lattice-gas model to examine the equilibrium composition of the surface layer, as a function of temperature, CO pressure and the Pd/Au ratio. We find that the surface Pd concentration for a nanoparticle of an Au/Pd alloy differs from that in a bulk sample. The difference is due mainly to the fact that in a nanoparticle the migration of Pd atoms to the surface depletes the bulk concentration while in a large sample; the bulk provides an infinite source of Pd atoms to populate the surface sites. This system is of interest because Pd/Au alloys are selective catalysts for vinyl acetate synthesis when the Pd concentration on the surface is very low.     

Surface characterization study of a Pd/Co3O4 methane oxidation catalyst

A surface characterization study using X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) has been performed on a 5 wt.% Pd/Co₃O₄ methane oxidation catalyst before and after exposure to a mixture of CH₄ and O₂ in N₂ at 250 °C for a period of 6 days. The primary peaks observed in the XPS survey spectra are the Co 2p, Pd 3d, O 1s and C 1s, along with Co, Pd and O Auger peaks. High-resolution Pd 3d spectra reveal that Pd exists on the surface predominantly as PdO, with no apparent change in chemical state during reaction. High-resolution XPS Co 2p and O 1s spectra reveal an accumulation of CoOOH and a depletion of CoO in the near-surface region during reaction. ISS analysis with intermittent 1-keV Ar⁺ sputtering was used to obtain depth profiles from the catalyst before and after reaction. The results indicate that the Pd/Co concentration ratio decreases with sputtering and that this ratio is larger for the as-prepared catalyst indicating that morphological changes occur during reaction. The ISS depth profile spectra obtained from the catalyst after reaction indicates the presence of an oxyhydroxide layer throughout the near-surface region. This observation is consistent with the XPS data indicating accumulation of hydroxide and oxyhydroxide species at the surface during reaction.Based on these data and the results of related studies, a reaction mechanism is proposed. In this mechanism, methane dissociatively chemisorbs to form a surface methoxy species and CoOOH. The remaining hydrogen atoms are stripped from the methoxy species leaving an active adsorbed C species which reacts with surface oxygen and a hydroxyl group to form an adsorbed bicarbonate ion which then decomposes to form CO₂ and a surface hydroxyl group. These hydroxyl groups also react to form H₂O and then more O₂ adsorbs dissociatively at the vacant sites.     

AES quantitative interpretation of the first stages of Pd2Si formation during Pd adsorption on Si(111) at room temperature

The quantitative analysis of the evolution of Pd and Si N(E) Auger peak amplitudes has been carried out as a function of Pd concentration on a Si(111) surface. Modelization of these evolutions has allowed us to conclude that the formation of the Pd₂Si silicide occurs from the beginning of Pd adsorption even at room temperature.     

Complete screening and quasiatomic MVV auger line shapes due to double core ionization

MVV spectra of Rh, Pd, and Ag were measured with and without ionization of their L3 levels. Extra (MMMVV) structure corresponds to the M45M45-->M45VV transition following the L3M45M45 transition. We interpret the MMMVV structure for Pd as quasiatomic in nature from its similarity to the corresponding Ag spectral shape and from its agreement with atomic calculations. The Pd quasiatomic MMMVV spectrum arises from a two final-state hole bound state in the Pd d band filled by screening of the core holes. These findings represent the first unambiguous observation of the influence of complete screening on spectral features.     

Growth of ultrathin Pd films on Al(001) surfaces

High-energy ion backscattering spectroscopy (HEIS) and X-ray photoelectron spectroscopy (XPS) were used to determine the growth mode and the interface structure of ultrathin Pd films deposited on Al(001) surfaces at room temperature. Measured Al and Pd surface peak areas for MeV He⁺ ions incident normal to the surface show that Pd atoms intermix with and displace Al substrate atoms. The mixing continues for Pd coverages from 0–5 monolayers, at which point a Pd metal film begins to grow on the alloy surface. XPS measurements of the Pd 3d photopeaks show a chemical shift that is consistent with the formation of an AlPd-like compound during the mixing phase, and Pd metal thereafter. HEIS results further reveal that the alloyed overlayer as well as the Pd metal film have some degree of axial alignment with respect to the Al substrate. The XPS intensity measurements are consistent with this two-stage growth model.     

Quantitative auger electron spectroscopy analysis of AgPd and NiPd alloys

The relationship between peak amplitude in derivative Auger spectra and alloy composition was investigated for AgPd and NiPd alloys. Measurements were performed on polished and sputter etched samples as well as on samples fractured in vacuo. For clean alloy surfaces and in the absence of sputtering, a linear relationship between peak amplitude of a given alloy component and atomic concentration was observed. Relative Auger peak amplitudes measured on sputter cleaned surfaces were different from those measured on fractured surfaces. Results were interpreted in terms of a simple model considering surface enrichment of the alloy component with the lower relative sputtering yield.     

Characterization of In/Pd and Pd/In/Pd thin films by ellipsometric, XRD and AES methods

In/Pd and Pd/In/Pd thin films were prepared by thermal evaporation on the SiO₂ substrate in a vacuum. The structural and optical properties of the films were investigated by means of X-ray diffractometry (XRD), Auger electron spectroscopy (AES) and spectroscopic ellipsometry (SE). Auger depth profile studies were performed in order to determine the composition of elements in the Pd-In systems. Interdiffusion of metals was detected at room temperature. Optical properties of Pd-In composite layers formed due to the interdiffusion were derived from ellipsometric quantities Ψ and Δ measured in the photon energy range 0.75-6.50 eV at different angles of incidence. The effective optical spectra show absorption peaks dependent on the composition of nonuniform films. The XRD patterns indicated formation of Pd_1−xIn_x intermetallic phases in the samples.