Ag on Mo(110) studied by AES and STM

Auger electron spectroscopy (AES) and scanning tunnelling microscopy (STM) have been used to investigate the growth behaviour of ultra-thin Ag films on a Mo(110) surface at room temperature. An analysis of AES and STM measurements indicates that three-dimensional (3D) growth of a Ag film is observed. For submonolayer coverage, the growth of Ag is mediated by a two-dimensional step-flow mechanism. During the initial stage of this growth, the first Ag layer nucleates and creates islands (average size of islands is about 180 ± 20 nm²) at Mo step edges. In the monolayer coverage range, the decoration of substrate steps by Ag can be distinguished by the presence of a fractional step of p₁ = 0.86 ± 0.6 Å height at the Ag–Mo boundary. As the sample is post-annealed to 700 K, the morphology of the surface changes. Step-flow growth in this case gives rise to a regular Ag nanostripe network attached to Mo(110) step edges. The corrugation profiles reveal the protrusion of silver nanostripes of thicknesses p₁ = 0.98 ± 0.16 Å and p₂ = 0.39 ± 0.06 Å for submonolayer and monolayer coverage ranges, respectively, above each single step of a Mo terrace morphology.     

Adsorption and reaction of bromine with Ag(110)

The adsorption and reaction of Br₂ with Ag(110) was studied with Auger electron spectroscopy, LEED, work function measurements and thermal desorption spectroscopy in the temperature range of 130–1000 K. Depending on Br coverage and crystal temperature, four different adsorption and reaction states could be detected. For fractional monolayer coverages, chemisorbed Br(ad) is found to be the most stable species. This adsorption state saturates for θ(Br) ? 0.75. In the chemisorption stage, two LEED patterns, a p(2 × 1) with θ(Br) ? 0.5 and a c(4 × 2) with θ(Br) ? 0.75, were observed. For higher Br₂ exposures and T = 130 K a layer-by-layer growth of AgBr is detected. At higher temperature, T > 190 K, there is evidence for a transformation from a 2D growth mechanism of AgBr into a 3D agglomeration of larger AgBr cluster. Molecularly adsorbed.     

Theoretical studies of chemisorbed oxygen on Ag(110)

The interaction of an oxygen atom with a 26-atom cluster model of the (110) face of Ag has been investigated with ab initio self-consistent-field and configuration-interaction theory. The SCF results for the bridge site (C_2v) predict $\text{r = 0.3}\text{A}\text{?}$ and ω_e = 327 cm^?1, in good agreement with the available experimental evidence. The calculated binding energy (D_e = 9 kcal/mole) is roughly an order of magnitude too small. The inclusion of electron correlation increases r_e and ω_e only slightly, but should have a dramatic effect on D_e. The ground state corresponds to a “surface oxide” state. The theoretical projected density-of-states curves exhibit “bonding” and “anti-bonding” O(2p) peaks, separated by ~ 6 eV, in good agreement with recent angle-resolved photoemission data.     

Adsorption of oxygen on W(110): II. The high coverage range

The structure and composition of the interaction layer between oxygen and a W(110) surface for oxygen coverages θ above 0.5 monolayers is studied with LEED, AES, thermal desorption and work function change measurements. Oxygen is adsorbed by depositing WO₂ followed by annealing. The results are interpreted in terms of a topmost layer consisting only of oxygen atoms followed by the formation of isolated three-dimensional WO₃ crystals after saturation of the two-dimensional oxidation layer at 15 × 10¹⁴ O atoms cm^?2. All available experimental evidence is compatible with this interpretation.     

Adsorption of water and methanol on GaAs(110) surfaces studied by ultraviolet photoemission

UV photoemission spectroscopy (UPS) with He 1 radiation (hν = 21.2 eV) has been used to study the interaction of H₂O and CH₃OH with GaAs(110) surfaces prepared by cleavage in ultrahigh vacuum (UHV). For H₂O two molecularly adsorbed phases can be distinguished at 300 K: at low coverage H₂O is chemisorbed by its oxygen lone-pair orbital to the surface whereas for higher exposures a less perturbed species which resembles more a “physisorbed” or condensed H₂O layer is found. At 180 K only the less perturbed species can be identified. Also CH₃OH is chemisorbed molecularly at lower coverage with its oxygen end to the GaAs surface. For higher exposures two additional emission bands are observed which are interpreted as due to the methoxy radical CH₃O resulting from a partial decomposition of CH₃OH.     

The adsorption of molecular oxygen species on Ag(110)

The adsorption of oxygen on the Ag(110) surface was examined at temperatures down to 123 K. In addition to the dissociatively adsorbed state which desorbed at 590 K, a second oxygen state desorbed at 190 K following adsorption at 150 K and below. This high temperature state appeared to form prior to the development of the low temperature state. The ratio of coverages of the two states was a strong function of both exposure and adsorption temperature. Isotopic exchange experiments indicated that the low temperature state was molecularly adsorbed. The desorption of the molecularly adsorbed oxygen exhibited complex kinetics due to interaction with adsorbed oxygen atoms.     

Adsorption behavior of iron phthalocyanine on a Ag（110） surface

An investigation on the growth behavior of FePc on a Ag(110) surface is carried out by using scanning tunneling microscopy(STM).At an FePc coverage of 3.5 ML,an ordered superstructure(densely packed) with a lateral shift is observed.The densely packed superstructure can be attributed to the substrate commensuration and the intermolecular van der Waals attractive interaction.The in-plane lateral shift in the superphase is specifically along the direction of [10] azimuth.The results provide a new perspective to understanding the intermolecular and the molecule-substrate interactions.     

Atomic chemisorption of chlorine on Ag(110) studied by high-resolution electron energy loss spectroscopy

We have studied atomic chemisorption at room temperature of chlorine on Ag(110) using high-resolution electron energy loss spectroscopy (HREELS), supplemented by XPS and LEED. The ClAg vibration energy (around 25 meV) and the line-width of this loss peak show well resolved variations with both chlorine coverage and substrate temperature T. The observed shift with T is related to the anharmonicity of the potential. Based on the Morse potential we derive an anharmonicity parameter x_a = 6.2 × 10⁻² for the (2 × 1)Cl-overlayer. This indicates that the anharmonicity is enhanced by about a factor of two as compared to the bulk. In contrast, we find x_a < 0.2 × 10⁻² for c(4 × 2)Cl. By comparison to other data we conclude that the (2 × 1)Cl-phase is a simple overlayer, with no significant reconstruction of the topmost substrate layer.     

The adsorption of ammonia on a Fe(110) single crystal surface studied by high resolution electron energy loss spectroscopy (EELS)

EELS spectra of ammonia adsorbed on a Fe(110) single crystal surface at 120 K reveal four different molecular adsorption states:1. At very low exposures (0.05 L) three vibrational losses at 345 cm^?1, 1170 and 3310 cm^?1 are observed which are attributed to the symmetric Fe-N stretching-, N-H₃ deformation and N-H₃ stretching modes of chemisorbed molecular ammonia, respectively. The observation of only three vibrational losses indicates an adsorption complex of high symmetry (C_3v).2. Further exposures up to 0.5 L cause the appearance of additional losses at 1450 cm^?1, 1640 cm^?1 and 3370 cm^?1. The latter two are interpreted as the degenerate NH₃ deformation and - stretching modes of molecularly adsorbed NH₃. The 1450 cm^?1 loss is a combination of the losses at 345 cm^?1 and 1105 cm^?1. The observation of 5 vibrational losses is consistent with an adsorption complex of C_s symmetry.3. In the exposure range from 0.5 to 2 L adsorption of molecular ammonia in a second layer is observed. This phase is characterized by a symmetric deformation mode at 1190 cm^?1 and by two additional very intense modes at 160 cm^?1 and 350 cm^?1 which are due to rotational and translational modes.4. Exposures above 2 L cause multilayer condensation of ammonia characterized by translational and rotational bands at 190 cm^?1, 415 cm^?1 and 520 cm^?1, and a symmetric deformation mode at 1090 cm^?1. A broad loss feature around 3300 cm^?1 is attributed to hydrogen bonding in the condensed layer.Thermal processing of a Fe(110) surface ammonia covered at 120 K leads to decomposition of the ammonia into hydrogen and nitrogen above 260 K. No vibrational modes due to adsorbed NH or HN₂ species were detected.     

Work function measurements with a high resolution electron energy loss spectrometer: Application to the interaction of oxygen with Ag(110)

The monochromatized electron beam of a high resolution electron energy loss (HREEL) spectrometer is used for accurate (±5 meV) measurement of the work function changes during exposure of a Ag(110) single crystal surface to oxygen. Absolute calibration of the results is made by comparison with Kelvin probe data. The procedure allows the precise determination of the electron impact energy, which is an important parameter for quantitative HREELS analysis. Furthermore, in the case of oxygen adsorbed on Ag(110), the occurrence of several LEED (n×1) superstructures enables a calibration of the HREELS data with respect to surface coverage.     

ELS study on chemisorbed state of CO on Cr(110)

The chemisorbed state of CO on a Cr(110) surface has been investigated at 300 K by electron energy loss spectroscopy (ELS) with the in-situ combined supplementary techniques. The ELS spectrum of the Cr(110) surface after CO adsorption is characterized by the peaks at 2, 4.4, 6–7, 9, 11, 14.5, 19 and 23 eV, and is found to be practically the same as that of the oxygen covered surface. The C-KLL Auger spectra obtained in the range 0.1–900 L CO agree with those of metal carbides. These results are considered to indicate that CO is dissociatively chemisorbed on the Cr(110) surface throughout the whole exposure region examined. The average sticking probability of CO on Cr(110) is 0.7 at below 0.5 L, and the maximum work function increase at 1 L is ~0.1 eV. The adsorbed state of O atoms produced from dissociative adsorption of CO is also discussed.     

Adsorption of ethylene on clean and oxygen precovered Cu(110) surfaces

UV photoemission spectroscopy (UPS) with He I and He II radiation is used to study the interaction of C₂H₄ with clean and oxygen precovered Cu(110) surfaces at 90 K. On the clean surface only-bonding of the C₂H₄ molecules is observed whereas preadsorbed oxygen causes a second molecular orbital to be involved in the chemisorption. This result is consistent with the differing behaviour of the work function change during thermal desorption of C₂H₄.     

Adsorption of CO on W(001) by high resolution electron spectroscopy

The vibrational modes induced by CO on W(001) at temperatures ? 350 K are detected by means of electron energy loss spectroscopy with resolution in the 6–7 meV range. Two β adsorption regimes are identified depending on coverage. Heating at various increasing temperatures reveals coverage dependant irreversible surface structure modifications. The β spectra after adsorption or desorption are discussed in terms of the usual questions of multiple β states, dissociation, and reconstruction. The α₁ and α₂ states are detected both by their WC and CO frequencies. A small signal is assigned to a new a-state, named α₃, which may explain some thermal desorption results.     

Cleavage of N-H bonds by active oxygen on Ag(110): I. Ammonia

Ammonia adsorbs without dissociation on clean Ag(110) with a binding energy of 11 kcal/mol. Coadsorption of ammonia and atomic oxygen at 105 K produces adsorbed hydroxyl groups and NH_x species. Coadsorption of ammonia and molecular oxygen leads to the stabilization of molecular oxygen, as is shown by the increase in the desorption peak temperature of dioxygen from 180 to 210 K. The reaction of ammonia with both forms of adsorbed oxygen produces the same products at the same temperatures. Water desorbs in a series of peaks at 310, 340, and 400 K resulting from hydroxyl recombination and hydrogen transfer from NH_x species to adsorbed oxygen atoms. NO and N₂ desorb together at 530 K. Oxygen recombination at 590 K only occurs following small ammonia doses such that excess oxygen persists on the surface. No hydrogen was seen to desorb under any reaction conditions. Vibrational spectroscopy shows that NH groups persist on the surface at temperatures well into the water desorption peak at 310 K and possibly to significantly higher temperatures, indicative of the difficulty of N-H bond cleavage by metallic silver.     

Adsorption and reaction of bromine with Ag(110): A photoemission study

The adsorption of bromine on the (110) surface of silver has been studied by ultraviolet (hυ = 21.2 and 40.8 eV) photoelectron spectroscopy in the temperature range of 100–300 K. Four different adsorption and reaction states could be detected. For fractional monolayer coverages Br₂ adsorbs dissociatively on the Ag(110) surface. The chemisorption of bromide leads to new emission features at about 3 and 5.2 eV below E_F, which are assigned as occupied antibonding structures (3 eV) and as bonding Br4p_{x, y} orbitals (5.2 eV). At 100 K, further bromide adsorption leads to the formation of an AgBr layer with molecular adsorbed bromine on top of this corrosion layer. The He I spectrum is dominated by structures at 3.5, 5.8 and 7.5 eV which are due to emission from the π_g, π_u and σ_g molecular orbitals of Br₂. The buildup of the AgBr layer is clearly demonstrated by desorbing the molecular bromine at about 150 K. The resulting spectrum of the AgBr layer shows peaks at 2.5 and 3.4 eV with p- and mixed-in d-character and peaks at 4.1, 5.2 and 6.1 eV which are primarily d-like. Heating of the AgBr layer up to 300 K results in a transformation from a 2D layer into a 3D agglomeration of larger AgBr clusters on top of a Br/Ag(110) chemisorption layer.     

Mechanisms for oxygen adsorption on the Si(110) surface studied by Auger electron spectroscopy

Oxygen adsorption on the Si(110) surface has been studied by Auger electron spectroscopy. For a clean annealed surface chemisorption occurs, with an initial sticking probability of ～6 × 10^?3. In this case the oxygen o_kll signal saturates and no formation of SiO₂ can be detected from an analysis of the Si L_2,3VV lineshape. With electron impact on the surface during oxygen exposure much larger quantities are adsorbed with the formation of an SiO₂ surface layer. This increased reactivity towards oxygen is due to either a direct effect of the electron beam or to a combined action of the beam with residual CO during oxygen inlet, which creates reactive carbon centers on the surface. Thus in the presence of an electron beam on the surface separate exosures to CO showed adsorption of C and O. For this surface subsequent exposure in the absence of the electron beam resulted in additional oxygen adsorption and formation of SiO₂. No adsorption of CO could be detected without electron impact. The changes in surface chemistry with adsorption are detectable from the Si L_2,3VV Auger spectrum. Assignments can be made of two main features in the spectra, relating to surface and bulk contributions to the density of states in the valence band.     

Adsorption of oxygen and hydrogen on Pt(111) studied with second-harmonic generation

The adsorption of oxygen and hydrogen on a Pt(111) surface has been studied with phase-sensitive Second-Harmonic Generation (SHG) signal detection. The SHG-signal change measured with p-in, p-out polarization during the adsorption of oxygen and hydrogen was found to be different in amplitude and phase for the two adsorbates. At the wavelength used (1064 nm), only a localized interaction between adsorbate and substrate is seen, leading to a linear dependence of the susceptibility on the coverage. Sticking coefficients,s, and their coverage dependence were determined. For hydrogen, a linear decrease ins with coverage was found; the initial sticking coefficient beings ₀=0.06 at a temperature ofT=130 K. For oxygen,s whows a quadratic decrease with coverage, strongly dependent on temperature, withs ₀=0.05 atT=350 K.A method based on these results is proposed, which would allow the determination of adsorbate coverages of coadsorption systems with SHG using phase-sensitive signal detection.Presented at the 129th WE-Heraues-Seminar on Surface Studies by Nonliner Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994