Electron spectroscopic studies of tin surface segregation on iron single crystal surfaces

AES, ELS, LEED and XPS investigations of the surface segregation of tin dissolved in a Fe-4wt%Sn alloy were performed in ultra-high vacuum at elevated temperatures. The three low indexed surface orientations (100), (110) and (111) were studied. In all cases, no dependence of the maximum tin surface coverage on temperature was detected within the temperature range from 450 to 650°C. An order-disorder transition was observed by LEED, AES and XPS for the (100) oriented surface during tin segregation. The binding state for the segregated tin atoms abruptly changes at the order-disorder transition as determined by XPS. Similar results were obtained for the (111) surface. A deviating behaviour was observed for the (110) surface orientation, where two different ordered hexagonal surface structures were detected by LEED during tin surface enrichment. The first structure is similar to the diamond structure of pure tin, and the second one corresponds to the formation of a thin layer of the intermetallic compound FeSn on the (110) surface. The electron binding energies of the segregated tin atoms determined by XPS increase with increasing tin coverage on the (110) oriented surface. ELS studies on (100) and (111) oriented surfaces saturated with segregated tin show in comparison with literature data of pure tin a surface plasmon loss peak but no signal for the corresponding bulk loss. An energy loss signal found only for the (110) surface at Sn saturation coverage seems to be characteristic of an intermetallic FeSn surface phase.     

Electron spectroscopic studies of clean and oxidized iron

X-ray photoelectron spectroscopy (XPS) and soft X-ray appearance potential spectroscopy (APS) together with Auger electron spectroscopy (AES) were used to study the electronic properties of clean and oxidized (Fe₃O₄) iron surfaces. The features arising from excitations of electrons from Fe 2p core levels are discussed consistently within the common one-electron picture (i.e. neglecting final state effects). For pure Fe the shape of the APS L₃ peak is evaluated taking into consideration the theoretical density of states above the Fermi level and is found to agree well with that observed. As a consequence it is shown that in this case the appearance potential is about 1 eV larger than the threshold energy for the excitation of a core electron to the Fermi level. Thus for $\text{2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ electrons this quantity results to be 704.8 eV from both XPS and APS techniques. Successive oxidation at 500°C leads to an increase of the appearance potentials of the Fe 2p levels by only 0.5 eV, whereas the positions of the corresponding XPS peaks are shifted by as much as 3.5 eV. However this apparent disagreement can be eliminated by taking into account the above mentioned effect concerning the appearance potentials from pure Fe and the fact that the threshold energies (which determine the appearance potentials) of the XPS signals are shifted only by 1.7 eV. This example demonstrates that considerable care has to be taken in discussing “binding energies” or “chemical shifts” as derived from different electron spectroscopic techniques. The observed splitting of the MVV Auger transition of Fe at 47 eV upon oxidation is interpreted in terms of the qualitative features of the valence band structure of Fe₃O₄ and ascribed to the participation of a cross-transition between O 2p and Fe 3p states.     

The interaction of oxygen and nitrogen with the niobium (100) surface: I. Morphology

Low energy electron diffraction has been used to investigate the reactions between nitrogen and oxygen and the (100) face of niobium. Several different oxygen containing surface structures were observed.     

Electron spectroscopic study of surface segregation and oxidation of Cu-In and Cu-Au alloys

XPS and AES techniques were employed to study the surface segregation and oxidation of Cu-1at%In alloy. Surface segregation of In has been observed with an enthalpy of segregation of about −34 kJ/mol. The surface oxidation of the Cu-In alloy at 480 K showed first a formation of Cu₂O on the alloy surface. The displacement reaction 3Cu₂O + 2In → 6Cu + In₂O₃ occurred on the alloy surface, on further heating of the oxidized surface in vacuum at 700 K. XPS and UPS techniques were employed to study the oxygen interaction with Cu-5at%Au and Cu-11at%Au alloys. At 300 K, oxygen was dissociatively chemisorbed on the Cu sites of the Cu-11% Au alloy surface, and the oxygen desorbed on heating. TDS study showed that desorption follows second order kinetics with an activation energy of desorption of about 75 kJ/mol.     

The interaction of oxygen and nitrogen with the niobium (100) surface: II. Reaction kinetics

Auger spectroscopy has been used to investigate the interactions of oxygen and nitrogen with both the (100) face niobium and with polycrystalline niobium. Sticking coefficients for both gases have been determined as a function of coverage. A temperature and concentration ependent segregation of oxygen at the surface has been observed even under conditions where the solid solubility of the bulk was not exceeded. A model to describe this segregation has been developed and extended to explain discrepancies in earlier investigations f the reaction of oxygen with niobium.     

High resolution electron energy loss spectroscopic study of the interaction of oxygen with magnesium single crystal surfaces.

From the beginning of the interaction of oxygen with the clean Mg(0001) and Mg(1$\text{1}$00) surfaces, two vibrational bands were measured by HREELS. The first one at 480 cm^?1 is attributed to atomic oxygen adsorbed at the surface. The second band at 620 cm^?1 is related to the stretching vibration of incorporated oxygen precursor to oxide formation. No specific difference was observed in the position and evolution of the two bands for both surfaces, but the electronic intensity reflected in the specular peak exhibited a totally different behaviour. The widths of the vibrational bands suggest a strong coupling with the continuum of electron-hole pairs of the metal.     

Surface sensitive spectroscopic study of the interaction of oxygen with Al(111) - low temperature chemisorption and oxidation

The interaction of an atomically clean Al(111) surface with O₂ has been studied using a combination of electron energy loss spectroscopy (EELS) and Auger spectroscopy (AES). Oxygen dissociatively adsorbs and occupies both surface and subsurface binding sites under all exposure conditions in the temperature range 122–700 K. Surface sites are preferentially occupied at low exposures, while higher exposures increasingly favor population of subsurface sites. Studies of O₂ adsorption at temperatures as low as 131 K have shown that formation of Al₂O₃ occurs at high oxygen exposures. The Al₂O₃ produced exhibits a 54 eV Auger transition and a characteristic vibrational spectrum with loss features at 430, 645, and 880 cm⁻¹. Argon ion bombardment of thin monolayer level Al₂O₃ layers leads to preferential loss of Al₂O₃ and a reduction in the subsurface-to-surface oxygen ratio. Electron bombardment of similar, thin Al₂O₃ layers is ineffective in inducing desorption of surface species, whereas thick Al₂O₃ layers are strongly influenced by electron bombardment, as judged from AES behavior. Qualitative models for O₂ adsorption, oxidative annealing, and damage by ion and electron bombardment are given.     

Study of the interaction of argon and nitrogen ions with the silicon dioxide surface

Angular dependences of the sputtering yield, surface layer composition, and changes in the mass spectra of residual atmosphere upon irradiation of silicon dioxide with argon and nitrogen ions are measured. It is found that the sputtering yield of SiO₂ bombarded by N ₂ ⁺ ions is almost two times higher than for Si. The sputtering yields of SiO₂ and Si irradiated with Ar ions are identical, although the binding energy of atoms in SiO₂ is almost two times higher than in Si. An analysis of the surface composition and residual atmosphere near the sample during its irradiation suggests that a chemical reaction is involved in SiO₂ sputtering. Molecules of SiO and NO gases form in the surface layer, whose subsequent desorption increases the SiO₂ sputtering rate.     

Atomistic simulation of the interaction of slow protons with an iron surface

Summary We have studied the dynamical behaviour of low-energy protons (1.0 eV≤E _in≤50 eV) interacting with a Fe {100} surface atT=300 K, by means of molecular-dynamics simulations. The inelastic energy losses have been taken into account by means of a friction term proportional to the projectile velocity and depending on the instantaneous local electronic density experienced by the projectile. For a given incident energy and irradiation geometry, we have estimated the particle and energy reflection coefficients and obtained a detailed evaluation of the different contributions (elastic and inelastic) to the energy loss of the reflected particles.     

A LEED/UPS study on the interaction of oxygen with a Ni(111) surface

Exposure of a Ni(111) surface to oxygen leads at first to the formation of a chemisorbed overlayer which is characterized by a 2 × 2-superstructure and a maximum in the photoemission spectrum (hv = 40.8 eV) centered at 5.6 eV below the Fermi level E_F. The emission from the Ni d-states is nearly unaffected at this stage of interaction. After high oxygen exposures the epitaxial growth of NiO can be identified from the LEED pattern. The corresponding photoelectron spectrum is strongly altered and exhibits close agreement with the transition energies as calculated by Messmer et al. for a NiO₆^10- -cluster.     

The interaction of oxygen with the Rh(111) surface a

The adsorption of oxygen on Rh(111) at 100 K has been studied by TDS, AES, and LEED. Oxygen adsorbs in a disordered state at 100 K and orders irreversibly into an apparent (2 × 2) surface structure upon heating to T? 150 K. The kinetics of this ordering process have been measured by monitoring the intensity of the oxygen $\text{(1,}\text{1}\text{2}\text{) LEED}$ beam as a function of time with a Faraday cup collector. The kinetic data fit a model in which the rate of ordering of oxygen atoms is proportional to the square of the concentration of disordered species due to the nature of adparticle interactions in building up an island structure. The activation energy for ordering is $\text{13.5 ± 0.5}\text{kcal}\text{mole}$. At higher temperatures, the oxygen undergoes a two-step irreversible disordering (T? 280 K) and dissolution (T?400K) process. Formation of the high temperature disordered state is impeded at high oxygen coverages. Analysis of the oxygen thermal desorption data, assuming second order desorption kinetics, yields values of 56 ± 2 kcal/ mole and 2.5 ± 10^?3 cm² s^?1 for the activation energy of desorption and the pre-exponential factor of the desorption rate coefficient, respectively, in the limit of zero coverage. At non-zero coverages the desorption data are complicated by contributions from multiple states. A value for the initial sticking probability of 0.2 was determined from Auger data at 100 K applying a mobile precursor model of adsorption.     

IR spectroscopic study of the effect of polymer nanofilm thickness on its surface density

The effect of the thickness (in the range 50–10,000 nm) of free-standing (separated from substrate) polystyrene (PS) films on their surface density was investigated by FTIR spectroscopy. For this, an approach has been employed for the first time than consists of analyzing the distortions of the IR band shape caused by anomalous dispersion of the refractive index in the vicinities of these bands. It was found that the surface density of PS films is halved as the film thickness changes from 1500 to 150 nm. The fact that the density starts to decrease in the micron range of film thickness rather than in the submicron range may suggest that there are important factors not taken into account by existing theoretical models for thin and ultrathin polymer films. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 63–67, January–February, 2008.     

The interaction of oxygen molecules with iron films studied with MIES,UPS and XPS

X-ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of oxygen molecules with iron films. Supplementarily, iron oxide was investigated for comparison.With XPS from the Fe 2p_3/2 range contributions of metallic Fe as well as Fe²⁺ and Fe³⁺ can be distinguished. During the interaction with oxygen an oxide film is formed on the iron surface. Nevertheless, XPS still shows metallic contributions even for a surface which is saturated with more than 10⁴ L. The oxide film hinders the dissociation of further impinging oxygen molecules.The interaction of He* atoms with iron oxide surfaces during MIES is dominated by Auger Neutralization. This surprising result follows from the high work function and the fact that intrinsic defects result in a Fermi level pinning to the conduction band.