Surface excitation probabilities in surface electron spectroscopies

The phenomenon of surface excitation is competitive in nature for elastic and other inelastic scattering processes in surface electron spectroscopies; the knowledge of influence of surface excitations in electron energy loss spectra is then essential for quantitative surface analysis with these spectroscopies. The inelastic scattering of an electron moving in the vicinity of a surface is considered in a self-energy formalism to estimate the contribution of surface excitation in electron-solid interactions via the total surface excitation probability. The formulation uses the optical bulk dielectric function and provides the spatial and angular dependence of the differential and total inelastic cross-sections. The kinetic energy range of probing electrons considered is 100-5000 eV and the numerical evaluation of total surface excitation probabilities are performed for several metals, Au, Ag, Cu, Ni, Fe and Ti; empirical formulae for the surface excitation probability are given for each of these materials and compared with experimental results for the surface excitation parameter. The total surface excitation probability is higher in Ag as compared to other metals under consideration, for identical conditions of electron-solid interactions.     

Many-body effects in the electron spectroscopies of incompletely filled bands

Summary Photoemission and Auger line shapes from almost completely filled bands have been widely discussed in recent years within a simplified model based on an Anderson Hamiltonian in which the virtual level shift due to the interactions is suitably compensated for. Up to now, the theory has been much more successful with XPS than with AES, and the reason for this was obscured by the lack of an exact solution and by the difficulty to assess the degree of validity of various approximate treatments that have been proposed. Here we present a Green’s function formalism that allows us to extend the closed band solution to the partially occupied case and lends itself to the exact numerical treatment of finite systems. By applying the theory to 27 and 125 atom clusters, we analyse the dependence of the spectra on hole-hole repulsionU with a degree of unfillingn _h≤0.25. We also consider the case when one of the spin subbands is full as a rough model for ferromagnetic metals. Correlation effects on the one-hole density of states produce a narrowing of the band region, while a split-off structure develops below the band forU comparable to the band width. The low-density approximation is good agreement with the exact results forn _h=0.1 and also forn _h=0.25 for small and moderateU. Our results on the Auger line shapes justify somewhat the suggestion by Haak and Bennetet al. that split-off states observed in photoemission must be discarded before computing the two-hole spectrum. Indeed self-energy corrections must be excluded also in bandlike cases, when the simple procedure of cutting off the unwanted structure is not applicable. This arises because, in a wide range of physical situations, the Auger line shape reflects the mutual scattering of undressed final-state holes.

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Riassunto Il modello teorico piú usato negli ultimi anni per le forme di riga di fotoemissione ed Auger di bande quasi completamente occupate si basa su un hamiltoniano di Anderson in cui lo spostamento del livello virtuale dovuto alle interazioni è opportunamente compensato. Finora la teoria ha dato risultati molto migliori per la fotoemissione che per lo spettro Auger. Le ragioni di ciò non sono chiare poiché non si dispone di una soluzione esatta ed è difficile valutare l’attendibilità delle varie approssimazioni note. Pertanto noi proponiamo un formalismo basato sulle funzioni di Green che permette, nel caso di aggregati finiti di atomi, di estendere la soluzione esatta, nota nel caso di bande chiuse, al caso di bande parzialmente occupate. Applicando il metodo a sistemi di 27 e 125 atomi, analizziamo la dipendenza degli spettri dalla repulsioneU tra lacune, per una concentrazione di lacunen _h≤0.25. Abbiamo considerato anche il caso in cui una delle sottobande di spin è completamente occupata come una prima approssimazione al problema di metalli ferromagnetici. Gli effetti di correlazione restringono il continuo nella densità di stati ad una particella e producono una struttura discreta sotto la banda seU è confrontabile con la larghezza della stessa. L’approssimazione di bassa densità è in buon accordo coi risultati esatti pern _h=0.1 ed anche pern _h=0.25 seU è piccolo o moderato. I nostri risultati sulla forma di riga Auger legittimano in qualche modo quanto suggerito da Haak e Bennetet al., e cioè che il picco satellite di fotoemissione deve essere soppresso nel calcolo della forma di riga Auger. Anzi, tutte le correzioni al propagatore ad un corpo, dovute agli effetti di correlazione, debbono essere escluse anche nel caso di spettri di tipo banda, dove, per l’assenza della struttura satellite in fotoemissione, il procedimento di Bennettet al. non è piú applicabile: infatti nella maggior parte dei casi d’interesse fisico, la forma di riga Auger riflette la dinamica di lacune non rinormalizzate.

     

Nonadiabatic quasiparticle dynamics in time resolved electron spectroscopies of surface bands

Surface localized electronic states constitute electronic environment for a variety of physical and chemical phenomena taking place on surfaces. Various processes of model catalytic reactions may be influenced or mediated by hot electrons and holes excited in quasi-two-dimensional bands occurring on a large number of metal surfaces. Here we discuss several important aspects of nonadiabatic dynamics of these excitations which may affect the measurements of surface electronic properties by ultrafast electron spectroscopies.     

UV degradability of polysilanes for nanoresists examined by electron spectroscopies and photoluminescence

The aim of this study was to elucidate the degradation mechanisms in polysilanes, especially one-dimensional polysilylenes, with respect to the search for suitable resists for silicon industrial nanotechnologies. To this end we used the combined methods of photoelectron spectroscopies — PES (UPS and XPS) and photoluminescence — PL. Films of aryl-methyl-substituted polysilane chain, poly[methyl(phenyl)silylene] (PMPSi), prepared by casting from benzene solution, were analysed by X-ray and UV-induced photoelectron spectroscopy. Photoelectron spectra were recorded from the pristine PMPSi surface and after the UV photodegradation. Pronounced changes were found in the HeI induced photoelectron spectra indicating redistribution of filled Si 3s-like and Si 3p-like states. The photodegradation by UV radiation for two different degradation wavelengths λ = 266 and 355 nm was examined also by PL. We concentrated on the PL study in the region of the σ*-σ excitonic deexcitation after major degradations, studying the disorder and dangling bonds (DB) created by the degradation process. The results of both complementary methods are interpreted in accordance with our recent paper [1], with the degradation process explained by two competing phenomena, i.e. the energy dependent exciton transport by diffusion process and Si-Si bond scission. Presented at the X-th Symposium on Suface Physics, Prague, Czech Republic, July 11–15, 2005.     

Determination of observable conduction band symmetry in angle-resolved electron spectroscopies: Non-symmorphic space groups

In angle-resolved photoemission, selection rules restrict the observavle final state symmetry. The rules for the initial state in inverse photoemission are the same. For cubic groups they are known (Hermanson [1]). In non-symmorphic space groups new rules apply. Here we show how to determine the observable final states for this class of space groups and work out explicitly the example of the graphite structure. The mathematical concepts are supported by direct experimental evidence obtained in normal photoemission from graphite.     

Atomically flat surface preparation for surface-sensitive technologies

Surface-sensitive measurements are crucial to many types of researches in condensed matter physics.However,it is difficult to obtain atomically flat surfaces of many single crystals by the commonly used mechanical cleavage.We demonstrate that the grind-polish-sputter-anneal method can be used to obtain atomically flat surfaces on topological materials.Three types of surface-sensitive measurements are performed on CoSi(001) surface with dramatically improved quality of data.This method extends the research area of surface-sensitive measurements to hard-to-cleave alloys,and can be applied to irregular single crystals with selective crystalline planes.It may become a routine process of preparing atomically flat surfaces for surface-sensitive technologies.     

A study of Al/Si(111)-cleaved interface by photoemission,Auger electron yield,and Auger electron spectroscopies

Photoemission, Auger electron yield, and Auger electron spectra are observed for Al/Si(111)-cleaved interfaces. The Al 3p derived state which becomes metallic at monolayer coverage is introduced near the top of the valence band. The Fermi level is stabilized in this metallic state. The present result favors the on-top geometry of Al atoms on a Si(111)-cleaved surface.     

Study of chemical states at intergranular fracture planes of iron-phosphorus alloys by auger and electron energy-loss spectroscopies

Auger and electron energy-loss spectroscopies (ELS) have been used to study chemical states at the fracture surfaces of iron-phosphorus alloys. The transgranular (TG) and intergranular (IG) fracture planes have similar Auger P LVV transition energies and similar Fe 3p loss energies. These indicate that phosphorus and iron atoms are dispersed atomically in layers segregated at IG planes. The energy separations between the inter-and intra-atomic Auger transition peaks in P LVV show that the TG and IG planes and Fe₃P have similar energy separations between the P 3p and Fe 3p levels. The layers segregated at IG planes are estimated to be equivalent to a monolayer, as indicated by the dependence of the loss energy of the valence-conduction-band transition on primary-electron kinetic energy from 200 to 500 eV. The phosphorus concentration in the segregated layers is saturated to ~ 20 at.% above a bulk phosphorus concentration of 2 at.%.     

Correlation of selected core-level spectroscopies

Spectral characteristics representing the distribution of unoccupied conduction-band states in the 3d transition-series metals Fe, Co, Ni and Cu, obtained using soft X-ray absorption (SXA), bremsstrahlung isochromat (BI) and characteristic isochromat (CI) methods, are related mathematically to those found in soft X-ray appearance-potential Spectroscopy (SXAPS) on the basis of the one-electron band approximation. These mathematical relationships are used to compute SXAPS spectra from reported experimental data obtained by the SXA, BI and CI methods. For the metals considered, the correlations between the computed and experimental SXAPS spectra are found to be good. The observed discrepancies are attributed to differences in the selection rules of the excitation processes, to the effect of the core vacancy on the final state, and to many-body phenomena which are not included in the simplified one-electron band model.     

Electron induced dissociation of CO on Ru(001): A study by thermal desorption and electron spectroscopies

CO adsorbed on Ru cannot convert thermally into a β-state of the kind observed on W and Mo — which is most probably dissociated CO — under CO pressures below 10^?5 Torr. Such a state can, however, be produced by electron impact onto a virgin CO layer adsorbed on Ru. This is shown using temperature-programmed desorption, UPS, XPS, XPS satellites, and XAES. A comparative discussion of the β-states on W and Ru yields rough estimates of the energies for desorption and conversion of CO on these metals; possible implications for catalytic reactions are mentioned.     

High energy spectroscopies and magnetism

We present a review of high energy spectroscopy (HES) techniques in the field of magnetism, and show that the use of HES techniques can give valuable information on magnetic systems. There is a wide range of HES techniques, so that a large number of parameters relevant to magnetism can be probed. This review will present some illustrations thereof.     

Surface characterization of catalysts using electron spectroscopies: Results of a round-robin sponsored by ASTM committee D-32 on catalysts

We report the results of a round-robin of measurements designed to evaluate the utility of Auger Electron Spectroscopy (AES) and X-ray Photoelectron Sp