Adsorption and decomposition of H2S on the Ge(100) surface

The adsorption and decomposition of H₂S on the Ge(100) surface is investigated. H₂S is a simple sulfur containing molecule that eventually decomposes to yield hydrogen gas and deposits sulfur on the germanium surface. The surface reactions of H₂S are investigated by ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, and temperature programmed desorption. Room temperature exposure of H₂S to Ge(100) results in dissociative adsorption which can be followed easily by ultraviolet photoelectron spectroscopy. Warming the H₂S exposed surface results in some molecular desorption and further decomposition of the adsorbed species. At saturation, 0.25 ML of H₂S decomposes generating 0.5 ML of atomic hydrogen. Above the hydrogen desorption temperature some etching of the germanium surface is observed by sulfur. The etch product, GeS, is subsequently observed in temperature programmed desorption experiments. Exposure of H₂S to the Ge surface at elevated temperatures leads to higher sulfur coverages. A sulfur coverage approaching 0.5 ML can be deposited at the higher exposure temperatures.     

Structural analysis of the β-SiC(100)-(2 × 1) surface reconstruction by automated tensor LEED

The atomic structure of the β-SiC(100)-(2 × 1) surface was analyzed using dynamical calculations of low energy electron diffraction (LEED) intensities measured with a video camera. Surface composition was monitored using Auger electron spectroscopy (AES). The LEED calculations utilized our recently developed automated tensor LEED method. The results indicate that the surface is terminated by a monolayer of silicon with the topmost silicon atoms forming asymmetric, buckled dimers.     

Hydrogen chemisorption on silicon (100) 2 × 1

Changes in the valence band density of states (DOS) of a (100) silicon surface that accompany he chemisorption of atomic hydrogen onto that surface are deduced from a study of the changes in the L_2,3VV Auger lineshape. Complementary changes in the conduction band DOS are inferred from changes in L_2,3VV-core-level characteristic loss spectra (CLS). The chemisorbed hydrogen layer is identified as the dihydride phase from low energy electron diffraction measurements. Upon hydrogen adsorption the DOS at the top of the valence band decreases and new energy levels associated with the Si-H bonds appear lower in the band. Assuming that the Auger signal from the hydrogen covered sample consists of a superposition of a signal from silicon atoms bonded to hydrogen in the dihydride layer and an elemental-Si signal from the substrate, a N(E) difference spectrum with features due only to the dihydride is obtained by subtracting the background corrected, loss deconvoluted L_2,3VV signal for a clean (100)Si surface rom the corresponding signal for the hydrogen covered surface. Comparisons of the energy position of the major peak in this difference spectrum with that of the main peak in a gas phase silane Si-L_2,3VV spectrum, and of the corresponding Auger energy calculated empirically, indicate a hole—hole interaction energy of ~8 eV for the two-hole final state in the gaseous system and zero for the dihydride surface system. Hydrogen induced changes in the conduction band DOS are less apparent than those of the valence band DOS with only the possibility of a decrease in the DOS at the bottom of the conduction band being inferred from the CLS measurements. Electron stimulated desorption of hydrogen from the dihydride layer is adduced from changes in the Auger lineshape under electron beam irradiation of the surface. Hydrogen induced changes in the near-elastic electron energy loss spectra (ELS) are also reported and compared with previously published ELS results.     

Oxygen adsorption on Ge(111) surface: II. Alkali metal-covered surfaces

Oxygen adsorption on an alkali metal (a.m.)-covered Ge(111) surface has been studied by means of Auger electron spectroscopy (AES), electron energy loss spectroscopy (ELS), thermal desorption (TD), and work function measurements (WF). It was found that the presence of a.m. results in enhancement of the oxygen adsorption rate. The initial values of the sticking coefficient, S₀, are exponential functions of the work function changes caused by the a.m. adsorption. It was shown that no germanium oxide phases are formed on an alkali-covered Ge surface at 300 K. The oxidation rate at high temperatures is limited by the rearrangement processes taking place in the surface GeO layer. The results obtained show that the alkali metal perturbs the GeO bond to a certain extent but no alkali oxide formation was observed at a.m. covertages under investigation.     

Oxygen adsorption on Ge(111) surface: I. Atomic clean surface

Oxygen adsorption on a clean Ge(111) surface has been studied in the temperature range 300–560 K by means of Auger electron spectroscopy (AES), thermal desorption (TD), work function (WF) measurements, and electron energy loss spectroscopy (ELS). The adsorption and WF kinetics at 300 K exhibit a shape different from those observed at higher adsorption temperatures. At 300 K oxygen only removes the empty dangling bond surface state, whereas at higher temperature new loss transitions involving chemically shifted Ge 3d core levels appear. The findings imply that at 300 K only a chemisorption oxygen state exists on the Ge(111) surface whereas the formation of an oxide phase requires higher temperatures. The shapes of the TD curves show that the desorption of GeO follows $\text{1}\text{2}$ order desorption kinetics.     

The co-adsorption of oxygen and hydrogen on Rh(111)

The co-adsorption of oxygen and hydrogen on Rh(111) at temperatures below 140 K has been studied by thermal desorption mass spectrometry, Auger electron spectroscopy, and lowenergy electron diffraction. The co-adsorption phenomena observed were dependent upon the sequence of adsorption in preparing the co-adsorbed overlayer. It has been found that oxygen extensively blocks sites for subsequent hydrogen adsorption and that the interaction splits the hydrogen thermal desorption into two states. The capacity of the oxygenated Rh(111) surface for hydrogen adsorption is very sensitive to the structure of the oxygen overlayer, with a disordered oxygen layer exhibiting the lowest capacity for hydrogen chemisorption. Studies with hydrogen pre-adsorption indicate that a hydrogen layer suppresses completely the formation of ordered oxygen superstructures as well as O₂ desorption above 800 K. This occurs with only a 20% reduction in total oxygen coverage as measured by Auger spectroscopy.     

Hydrogen adsorption on silicon (1 1 1) surfaces studied by Auger electron spectroscopy

The adsorption of atomic hydrogen on the (1 1 1) planes of silicon single crystals is studied by Auger Electron Analysis, using the decrease of the silicon Auger peak heigh as a measure of the hydrogen coverage. The zero coverage sticking coefficient is found to be 3 × 10^?4.     

Substitutional adsorption of K on Fe(100)

The adsorption of potassium on Fe(100) was studied by time-of-flight forward scattering and recoiling spectroscopy (TOF-SARS), low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). After heating to 650 K of the potassium saturated surface the formation of a p(3 × 3) potassium superstructure was observed by LEED. TOF-SARS experiments ruled out the adsorption of potassium in the on-top, bridge and four-fold hollow site. The only site which is in agreement with all experimental results is the substitutional site where K replaces an Fe atom of the topmost layer of the crystal. This is the first time a substitutional adsorption site has been found on a bcc surface. On an fcc surface such an adsorption site has been found recently for adsorption of sodium and potassium on Al(111).     

Thermal decomposition of 1,1-dimethylhydrazine on Si(100)-2 × 1

The surface reaction of 1,1-dimethylhydrazine (DMH) with Si(100) has been studied with temperature programmed desorption spectroscopy (TPD), temperature programmed static secondary ion mass spectrometry (TPSSIMS), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Adsorption of DMH on Si(100) at 170 K followed by annealing to 1100 K results in significant decomposition to form surface carbide and nitride. TPD results show that the only gas phase desoprtion products are hydrogen and dimethylamine. Furthermore, decomposition occurs over a broad temperature range; XPS and TPSIMS results indicate C---N bond cleavage beginning at 400 K and by 600 K, all the C---N bonds have dissociated. We propose a molecular level mechanism that involves partial decomposition upon adsorption followed by extensive bond cleavage to form surface carbide and nitride.     

Vibrational characterization of carbon monoxide oxidation on the Pt(111) surface

The surface reaction between coadsorbed carbon monoxide and atomic oxygen has been characterized using high resolution electron energy loss spectroscopy, coupled with temperature programmed reaction spectroscopy on a Pt(111) surface characterized using Auger electron spectroscopy and low energy electron diffraction. Preferential oxidation of bridge bonded CO is not observed despite the fact that bridge bonded CO is adsorbed less vigorously than linearly bound CO. Saturation of the Pt(111) surface with one quarter of a monolayer of atomic oxygen completely suppresses the adsorption of bridge bonded CO. However, substantial coverages of bridge bonded CO can be coadsorbed if the Pt(111) surface is only partially saturated with atomic oxygen. The vibrational data for reaction of coadsorbed CO and atomic oxygen is consistent with a reaction mechanism involving reaction of mobile CO along oxygen island perimeters.     

Direct observation of the surface segregation of Cu in Pd by time-resolved positron-annihilation-induced Auger electron spectroscopy

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to τ=1.38(0.21) h, and the final segregated configuration was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.     

Hydrogen chemisorption on the 100 (2 × 1) surfaces of Si and Ge

This paper combines a theoretical study of the Si(100) surface having a monolayer of atomic hydrogen chemisorbed to it with an experimental study of the analogous Ge(100) and Ge(110) surfaces. In the theoretical work the underlying (100) silicon surface is taken to be reconstructed according to the Schlier-Farnsworth-Levine pairing model with the hydrogen located on the unfilled tetrahedral bonds of this structure. Self-consistent calculations of the electronic potential, charge density, spectrum, and occupied surface density of states are carried out. The force on the hydrogen atoms is then calculated using the Hellman-Feynman theorem. This force is found to be close to zero, confirming that the hydrogen atoms are indeed at the equilibrium position for the chosen silicon geometry. Features in the calculated photoemission spectrum for the Si(100) 2 × 1 : H surface are discussed in terms of related features in the photoemission spectrum of Si(111) : H, but are found not to agree with the previously measured photoemission spectrum of Si(100) 2 × 1 : H. Measured photoemission and ion-neutralization spectra for Ge(100) 2 × 1 : H agree in their major features with what is calculated for Si(100) 2 × 1 : H, however, suggesting that the Ge(100) 2 × 1 : H surface is reconstricted according to the pairing model. Similarly, measured spectra for clean Ge(100) 2 × 1 agree with calculations for the row dimerized Si(100) surface.     

Oxidation and thermal reduction of the Cu(1 0 0) surface as studied using positron annihilation induced Auger electron spectroscopy (PAES)

Changes in the surface of an oxidized Cu(1 0 0) single crystal resulting from vacuum annealing have been investigated using positron annihilation induced Auger electron spectroscopy (PAES). PAES measurements show a large increase in the intensity of the annihilation induced Cu M_2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The intensity then decreases monotonically as the annealing temperature is increased to ∼600 °C. Experimental probabilities of annihilation of surface-trapped positrons with Cu 3p and O 1s core-level electrons are estimated from the measured intensities of the positron annihilation induced Cu M_2,3VV and O KLL Auger transitions. Experimental PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface, surface reconstructions, and electron-positron correlations effects. The effects of oxygen adsorption on localization of positron surface state wave function and annihilation characteristics are also analyzed. Possible explanation is proposed for the observed behavior of the intensity of positron annihilation induced Cu M_2,3VV and O KLL Auger peaks and probabilities of annihilation of surface-trapped positrons with Cu 3p and O 1s core-level electrons with changes of the annealing temperature.     

Molecular and atomic oxygen adsorption on the kinked Pt(321) surface

Oxygen adsorption and desorption were characterized on the kinked Pt(321) surface using high resolution electron energy loss spectroscopy, thermal desorption spectroscopy and Auger electron spectroscopy. Some dissociation of molecular oxygen occurs even at 100 K on the (321) surface indicating that the activation barrier for dissociation is smaller on the Pt(321) surface than on the Pt(111) surface. Molecular oxygen can be adsorbed at 100 K but only in the presence of some adsorbed atomic oxygen. The dominance of the v(OO) molecular oxygen stretching mode in the 810 to 880 cm^?1 range indicates that the molecular oxygen adsorbs as a peroxo-like species with the OO axis parallel or nearly parallel to the surface, as observed previously on the Pt(111) surface [Gland et al., Surface Sci. 95 (1980) 587]. The existence of at least two types of peroxo-like molecular oxygen is suggested by both the unusual breadth of the v(OO) stretching mode and breadth of the molecular oxygen desorption peak. Atomic oxygen is adsorbed more strongly on the rough step sites than on the smooth (111) terraces, as indicated by the increased thermal stability of atomic oxygen adsorbed along the rough step sites. The two forms of adsorbed atomic oxygen can be easily distinguished by vibrational spectroscopy since oxygen adsorbed along the rough step sites causes a v(PtO) stretching mode at 560 cm^?1, while the v(PtO) stretching mode for atomic oxygen adsorbed on the (111) terraces appears at 490 cm^?1, a value typical of the (111) surface. Two desorption peaks are observed during atomic oxygen recombination and desorption from the Pt(321) surface. These desorption peaks do not correlate with the presence of the two types of adsorbed atomic oxygen. Rather, the first order low temperature peak is a result of the fact that about three times more atomic oxygen can be adsorbed on the Pt(321) surface than on the Pt(111) surface (where only a second order peak is observed). The heat of desorption for atomic oxygen decreases from about 290kJ/mol (70 kcal/mol) to about 196 kJ/mol (47 kcal/mol) with increasing coverage. Preliminary results concerning adsorption of molecular oxygen from the gas phase in an excited state are also briefly discussed.     

Amorphous SiC film formation on Si(100) using electron beam excitation

The effect of electron impact on methylsilane (CH₃SiH₃) conversion to amorphous-Si_0.5C_0.5:H (a-Si_0.5C_0.5:H) films on Si(100) has been studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and low energy electron diffraction (LEED). It is found that electron impact greatly enhances CH₃SiH₃ decomposition on Si(100) at both 90 K and 300 K, resulting in a-Si_0.5C_0.5:H thin film formation. Thermal annealing of the film causes hydrogen desorption and amorphous silicon carbide (a-SiC) formation. Upon annealing to temperatures above 1200 K, the a-SiC film became covered by a thin silicon layer as indicated by AES studies. Ordered structures are not produced by annealing the a-SiC up to 1300 K.     

The adsorption of sulfur on the tungsten (110) surface

The adsorption and desorption of S on a W(110) surface is studied by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), work function change (δφ) measurements and thermal desorption spectroscopy (TDS). The evolution of the structure with coverage θ is quite different from that reported for S on Mo(110) and — at low coverages — from that of Te on W(110). At low coverages the structure indicates complex lateral interactions. The bonding changes with coverage similar to S on W(100). Evidence for more complex desorption kinetics than assumed in the past is presented.     

The adsorption of Xe and CO on Au(100)

The adsorption of Xe and CO on Au(100) has been studied by LEED, Auger electron spectroscopy, electron energy loss spectroscopy (EELS) and surface potential measurements. The physical adsorption of xenon showed successive stages preceding the completion of a monolayer. The heat of adsorption was 22 (±2) kJ mol^?1 and the maximum surface potential was 0.45 V. Carbon monoxide gave a surface potential of 0.85 V at the highest coverage reached. The heat of adsorption showed a continuous fall from an initial value of 58 (±3) kJ mol^?1 as the coverage increased. Ordered adsorption structures were not observed in LEED for either Xe or CO. The EEL spectrum of clean Au(100) agreed well with spectra of polycrystalline gold. New loss features observed with adsorbed Xe and CO are discussed.     

Adsorption and dissociation kinetics of alkanes on CaO(100)

The adsorption kinetics of ethane, butane, pentane, and hexane on CaO(100) have been studied by multi-mass thermal desorption (TDS) spectroscopy. The sample cleanliness was checked by Auger electron spectroscopy. A molecular and dissociative adsorption pathway was evident for the alkanes, except for ethane, which does not undergo bond activation. Two TDS peaks appeared when recording the parent mass, which are assigned to different adsorption sites/configurations of the molecularly adsorbed alkanes. Bond activation leads to desorption of hydrogen and several alkane fragments assigned to methane and ethylene formation. Only one TDS feature is seen in this case. Formation of carbon residuals was absent.     

The interaction of H2S with Si(111) 7 × 7 surfaces by energy loss and Auger electron spectroscopies

Low energy electron loss spectroscopy (ELS) and Auger electron spectroscopy (AES) have been applied for the studies of the interaction of H₂S molecules with Si(111)7 × 7 surfaces. The observations are consistent with the interpretation that the room temperature non-dissociative adsorption state of H₂S molecules changes substantially after annealing at 550°C, resulting in the desorption of hydrogen and the covalent bond formation between silicon and sulfur atoms. The silicon disulfide films formed on Si(111) surfaces have been identified by the characteristic loss peaks in comparison with those of silicon dioxide.     

Adsorption and desorption of ammonia,hydrogen, and nitrogen on ruthenium (0001)

The adsorption of ammonia, hydrogen, and nitrogen on a Ru(0001) surface have been investigated by Auger electron spectroscopy, low-energy electron diffraction, and thermal flash desorption. The adsorption of ammonia on Ru(0001) can be divided into a low temperature mode (100 K) and a higher temperature mode (300–500 K). For a crystal temperature of 100 K the ammonia adsorbs into two weakly bound molecular γ states with s = 0.2. The ammonia desorbs as NH₃ molecules with desorption energies of 0.32 and 0.46 eV. At 300–500 K adsorption occurs via an activated process with a low sticking probability (s ? 2 × 10^?4).This adsorption is accompanied by dissociation and formation of an apparent (2 × 2) LEED pattern. Hydrogen adsorbs readily (s = 0.4) on Ru(0001) at 100 K and desorbs with 2nd order kinetics in the temperature range 350–450 K. Nitrogen does not appreciably adsorb on Ru(0001) even at 100 K; maximum nitrogen coverage obtained was estimated to be <2% of a monolayer. Changes in the ammonia flash desorption spectra after hydrogen preadsorption at 100 K will be discussed.