A LEED, TPD and HREELS investigation of NO adsorption on Sn/Pt(111) surface alloys

The adsorption of NO on Pt(111), and the (2 × 2)Sn/Pt(111) and (√3 × √3)R30°Sn/Pt(111) surface alloys has been studied using LEED, TPD and HREELS. NO adsorption produces a (2 × 2) LEED pattern on Pt(111) and a (2√3 × 2√3)R30° LEED pattern on the (2 × 2)Sn/Pt(111) surface. The initial sticking coefficient of NO on the (2 × 2)Sn/Pt(111) surface alloy at 100 K is the same as that on Pt(111), S₀ = 0.9, while the initial sticking coefficient of NO on the (√3 × √3)R30°Sn/Pt(111) surface decreases to 0.6. The presence of Sn in the surface layer of Pt(111) strongly reduces the binding energy of NO in contrast to the minor effect it has on CO. The binding energy of β-state NO is reduced by 8–10 kcal/mol on the Sn/Pt(111) surface alloys compared to Pt(111). HREELS data for saturation NO coverage on both surface alloys show two vibrational frequencies at 285 and 478 cm⁻¹ in the low frequency range and only one N-O stretching frequency at 1698 cm⁻¹. We assign this NO species as atop, bent-bonded NO. At small NO coverage, a species with a loss at 1455 cm⁻¹ was also observed on the (2 × 2)Sn/ Pt(111) surface alloy, similar to that observed on the Pt(111) surface. However, the atop, bent-bonded NO is the only species observed on the (√3 × √3)R30°Sn/Pt(111) surface alloy at any NO coverage studied.     

An investigation of the Si(111)−(√3 × √3)R30°−Ag surface by Li impact collision ion scattering spectroscopy

The Si(111)−(√3 × √3)R30°−Ag surface has been investigated using the technique of Li⁺ impact collision ion scattering spectroscopy. Typical LEED √3 domain sizes were estimated to be on the order of 150 Å for a 1 ML coverage of Ag, with the √3 structure persisting for coverages of Ag up to 35 ML. Silver islanding was found to influence the appearance of the 5 keV Li⁺ ICISS angular scans even for 1 ML coverages of Ag deposited at 480°C. A detailed structural analysis of the Si(111)−√3−Ag surface (0.25 ML deposition) involved the comparison of 5 keV Li⁺ ICISS experimental data along the [11 ], [ 10] and [2 1] azimuths with computer simulations of the scattered ion intensities based on previously proposed models for the √3 surface. Nine structurally different models were tested, and only the missing-top-layer (MTL) and the honeycomb-chained-trimer (HCT) models were found to be consistent with all the experimental results. An estimate of 0.4 Å for the maximum downward vertical displacement of the Ag atoms with resect to the surface Si atoms in the MTL model is made. The effects of increased thermal vibrational amplitude in the simulation of Si---Ag shadowing effects is also discussed. The interpretations of previous noble gas ICISS results are shown to be inconsistent with the present alkali metal ICISS study of the √3 surface.     

The atomic geometries of the ordered (2 × 2) and (√3 × √3)R30° phases of K, Rb, and Cs on Rh(111) in comparison with Ru(0001)

The local adsorption geometries of K, Rb and Cs in the (√3 × √3)R30° and (2 × 2) phases on a Rh(111) surface at coverages of 0.33 and 0.25 ML, respectively, are determined by analyzing LEED intensity data. For all (√3 × √3)R30° phases investigated, the three-fold hcp site is found. For the (2 × 2) overlayer, K remains in the hcp position, while Cs favors the on-top position. For the case of Rb-(2 × 2), LEED analysis suggests occupation of the unusual two-fold bridge site. Since LEED analysis of the Rb-(2 × 2) phase is not completely conclusive, additional experimental evidence is necessary to firmly establish this adsorption geometry.     

The adsorption of CO on Pt(111) studied by infrared-reflection-adsorption spectroscopy

The adsorption of CO on Pt(111) between 85K and 300K has been studied by infrared-reflection-absorption spectroscopy together with TPD and LEED. The intensity of the absorption band due to the CO stretch of the linear species shows a maximum at the formation of the (√3 × √3)R30° LEED pattern followed by a minimum at the c(4×2) structure during the adsorption of CO at low temperatures (150K). The absorption band due to the C-O stretch of the bridging species appears only after the formation of the (√3 × √3)R30° pattern and reaches maximum intensity at the c(4×2) structure. Adsorption of CO to higher coverages (corresponding to the compression structures) broadens and shifts this absorption band. At higher temperatures (150K) a third peak is observed at 40cm⁻¹ below the peak due to the bridging species and is attributed to adsorption in the three-fold sites. At 300K both peaks in this region are very broad. The intensity data differs from that measured with EELS (ref.1) and favors a “faultline” structure of the type proposed by Avery (ref.2). Together with the additional information from bandwidths it is possible to distinguish between the various structural models. The results obtained here may also be important in explaining data from other systems such as CO/Cu.     

Formation of and phase transitions in electrodeposited tellurium atomic layers on Au(1 1 1)

Detailed studies of the structures formed by the electrodeposition of atomic layers of Te on Au(1 1 1) surfaces from aqueous solutions were performed using in situ scanning tunneling microscopy (STM), as well as by UHV-EC techniques such as low energy electron diffraction and Auger electron spectroscopy. There are two features in the voltammetry that may be considered underpotential deposition (UPD). However, from the voltammetry, it is clear that the deposition process is kinetically slow, and from this study it appears that several atomic layer structures are actually formed at overpotentials. Prior to deposition, a surface excess of a tellurium oxide species coats the surface. This layer is then converted to a Au(1 1 1)(√3×√3)R30°–Te structure with an array of domain walls, at 1/3 ML. The initial structure appears to have a symmetric array of walls, resulting in a (13×13) periodicity, which then converts to a less symmetric structure where the domain walls form rhombi, with a larger periodicity. During the second UPD feature, the coverage increases, forming a (√7×√13) unit cell at 0.36 ML and then a (3×3) at 0.44 ML. Commensurate with the formation of these higher coverage structures, a roughening transition takes place, where the surface becomes pitted, resulting in about 40% of the surface being covered with single atom deep pits. This process appears to be related to the pits formed in the surfaces of self-assembled monolayers (SAM) of thiols on Au surfaces, and layers of Se and S on Au surfaces. Several theories have been suggested to account for these pits. The model that appears to best explain the pits is based on shrinking of the size of the underlying Au atoms, reconstructing the underlying Au. There also appears to be a high coverage structure, near 0.9 ML, that forms at potentials near where the (3×3) forms, but only by holding the potential for an extended period of time. Subsequent dissolution of this high coverage structure produces domains of disordered Te atoms, which gradually decrease in coverage until the (3×3) is again formed at 0.44 ML.     

Surface structures of S/Ni(111) in (√3 × √3 )R30° and (5√3 × 2) phases studied by surface extended X-ray absorption fine structure spectroscopy

The local surface structures of S/Ni(111) in the ( √3 × √3) R30° and (5√3 × 2) phases have been investigated by means of polarization-dependent sulfur K-edge surface EXAFS. In the (√3 × √3 ) R30° phase, sulfur adatoms are found to occupy threefold hollow sites with a S---Ni distance of 2.13 Å and an inclination angle ω of the Sz.sbnd;Ni bonds at 44° from the surface plane. In contrast, in the (5√3 × 2) phase, it is determined that the Sz.sbnd;Ni bond is longer, 2.18 Å, more inclined, ω = 31°, and that the coordination number is not 3 but 4. These results strongly support a picture involving reconstruction of the top nickel layer to form a rectangular structure. Consideration of several models proposed for the (5√3 × 2) phase leads to one which is compatible with both the present results and results recently reported using STM.     

Oxygen induced reconstruction of (h11) and (100) faces of copper

A LEED and AES study on oxygen adsorption on Cu(100) and (h11) faces with 5 h 15 has been performed under various adsorption conditions (220 K T 670 K and 1 × 10⁻⁸ P 6 × 10⁻⁵ Torr of oxygen). The dependence of adsorption temp on the oxygen surface superstructures is pointed out. At least, three oxygen surface states exist on a Cu(100) face. For low temperature exposures to oxygen, under conditions of slow surface diffusion, on the (100) face, two oxygen surface phases exist: a “four spots” and a c(2 × 2) superstructure, both observed even at saturation coverage; on all the stepped faces, a c(2 × 2) appears and no faceting is observed. For high temperature exposures, on the (100) face, two oxygen superstructures are observed, a “four spots” followed by a (2√2 × √2)R45° at higher coverages; on all the stepped faces, surface diffusion is activated and oxygen induced faceting occurs. The appearance of faceting is associated with the onset of the formation of the (2√2 × √2)R45° structure on the (100) face. The oxygen induced faceting and the oxygen surface meshes are reversible with coverages. At saturation coverage, a non-reversible surface transition between the c(2 × 2) and (2√2 × √2)R45° superstructures is observed at 420 ± 20 K. The importance of impurity traces on the surface meshes is emphasized. Oxygen coverage at saturation is independent of the studied faces and adsorption temperature. Faceting occurs at a critical coverage value, whatever the stepped faces and adsorption temperature are. Models of the oxygen structure on the (h10) stepped faces are discussed.     

An STM study of the adsorption of Pb on Cu(100): formation of an ordered surface alloy

The adsorption of Pb on Cu(100) from 0 to 1 ML was investigated by UHV scanning tunneling microscopy. We obtained atomic resolution images of the different superstructures which appear at 300 K with increasing coverage (c(4 × 4), c(2 × 2) and c( √2)R45°). We confirm recent results and propose, partly on the basis of low temperature studies, new arguments in favour of an incorporation of lead atoms in the surface layer of copper for low coverage. We demonstrate that the c(4 × 4) superstructure corresponds to an ordered surface alloy of Pb₃Cu₄ composition, by investigating separately the alloying and de-alloying transitions. De-alloying occurs during the first-order transition between the c(4 × 4) and c(2 × 2) superstructures.     

Deposition of lead iodide films on Rh(1 0 0) electrodes from colloidal solutions––the effect of an iodine adlayer

The growth of PbI₂ precipitates on single crystal substrates from colloidal solutions has been investigated with in air scanning tunneling microscopy and synchrotron-based X-ray photoelectron spectroscopy. The PbI₂ growth on Rh(1 0 0) results in nano-clusters with lateral dimensions between 30 and 60 Å, consistent with earlier reports. However, the growth of PbI₂ on a well-ordered iodinated Rh(1 0 0), denoted as (√2×√2)R45°-I, leads to atomically smooth PbI₂ films having a hexagonal symmetry with lattice constant identical to the bulk value of 4.5 Å. The heteroepitaxy is believed to be effected by the atomic iodine monolayer that helps to accommodate large lattice mismatch between PbI₂ and Rh surface with short-range van der Waals interaction.     

A multitechnique surface science examination of Sn deposition on Pt(100)

Interfaces prepared by vapor deposition of Sn onto Pt(100) surfaces have been examined using the following techniques: Auger electron and X-ray photoelectron spectroscopy (AES and XPS), low-energy electron diffraction (LEED), and low-energy ion surface scattering (LEISS) with Ne⁺ ions. Tin deposition was conducted at 320 and 600 K, and the surface composition and order was examined as a function of further annealing to 1200 K. The AES uptake plots (signal versus deposition time) indicate that the Sn growth mode can be described by a layer-by-layer process only up to one adayer at 320 K. Some evidence of 3D growth is inferred from LEED and LEISS data for higher Sn coverages. For deposition at 600 K, AES data indicate significant interdiffusion and surface alloy formation. LEED observations (recorded at a substrate temperature of 320 K) show that the characteristic hexagonal Pt(100) reconstruction disappears with Sn exposures of 4.6 × 10¹⁴ atoms cm² (θ_Sn = 0.35 monolayer (ML)). Further Sn deposition results in a c(2 × 2) LEED pattern starting at a coverage of slightly above 0.5 ML. The c(2 × 2) LEED pattern becomes progressively more diffuse with increasing Sn exposure with eventual loss of all LEED features above 2.2 ML. Annealing experiments with various precoverages of Sn on Pt(100) are also described by AES, LEED, and LEISS results. For specific Sn precoverages and annealing conditions, c(2 × 2), p(3√2 × √2)R45°, and a combination of the two LEED patterns are observed. These ordered LEED patterns are suggested to arise from ordered PtSn surface alloys. In addition, the chemisorption of CO and O₂ at the ordered annealed Sn/Pt(100) surfaces was also examined using thermal desorption mass spectroscopy (TDMS), AES, and LEED.     

LEED structure determination of the Ni(1 1 1)(√3×√3)R30°-Sn surface

Quantitative low energy electron diffraction has been used to determine the structure of the Ni(1 1 1)(√3×√3)R30°-Sn surface phase. The results confirm that the surface layer comprises a substitutional alloy of composition Ni₂Sn as previously found by low energy ion scattering (LEIS), and also shows that there is no stacking fault at the substrate/alloy interface as has been found in (√3×√3)R30°-Sb surface alloys on Ag and Cu(1 1 1). The surface alloy layer is rumpled with the Sn atoms 0.45 ± 0.03 Å higher above the substrate than the surrounding Ni atoms. This rumpling amplitude is almost identical to that previously reported on the basis of the LEIS study. Comparison with similar results for Sn-induced surface alloy phases on Ni(1 0 0) and Ni(1 1 0) shows a clear trend to reduced rumpling with reduced surface atomic layer density, an effect which can be rationalised in terms of the different effects of valence electron charge smoothing at the surface.     

Surface structure evolution during Sb adsorption on Si(1 1 1)–In(4×1) reconstruction

The Sb adsorption process on the Si(1 1 1)–In(4×1) surface phase was studied in the temperature range 200–400 °C. The formation of a Si(1 1 1)–InSb (2×2) structure was observed between 0.5 and 0.7 ML of Sb. This reconstruction decomposes when the Sb coverage approaches 1 ML and Sb atoms rearrange to and (2×1) reconstructions; released In atoms agglomerate into islands of irregular shapes. During the phase transition process from InSb(2×2) to Sb (θ_Sb>0.7 ML), we observed the formation of a metastable (4×2) structure. Possible atomic arrangements of the InSb(2×2) and metastable (4×2) phases were discussed.     

Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

The growth mode of aluminium on silver (111)

The geometric and electronic structures occuring during the growth of Al on a single crystal Ag(111) surface have been studied using a combination of low energy electron diffraction (LEED), Auger electron spectroscopy (AES), energy loss spectroscopy (ELS) and work function measurements. The Auger signal versus deposition time plots, which were used to monitor the growth mode, are shown to behave in an identical fashion to that expected for layer-by-layer (Frank-van der Merwe) growth. LEED was used to determine the lateral periodicity of thin Al films and shows that Al forms, at very small coverages, 2D islands which have the same structure as the Ag(111) substrate and which grow together to form the first monolayer. At substrate temperatures of 150 K a well defined (1 × 1) structure with the same orientation as the underlying Ag(111) can be seen up to at least 12 ML. After completion of the third monolayer the ELS spectrum approached that observed for bulk aluminium. At a coverage of 3 ML the work function decreases by 0.4 eV from the clean silver value.     

The structure of oxygen on Cu(1 0 0) at low and high coverages

The local adsorption structure of oxygen on Cu(1 0 0) has been studied using O 1s scanned-energy mode photoelectron diffraction. A detailed quantitative determination of the structure of the 0.5 ML (√2×2√2)R45°-O ordered phase confirms the missing-row character of this reconstruction and agrees well with earlier structural determinations of this phase by other methods, the adsorbed O atoms lying only approximately 0.1 Å above the outermost Cu layer. At much lower coverages, the results indicate that the O atoms adopt unreconstructed hollow sites at a significantly larger O–Cu layer spacing, but with some form of local disorder. The best fit to these data is achieved with a two-site model involving O atoms at Cu–O layer spacings of 0.41 and 0.70 Å in hollow sites; these two sites (also implied by an earlier electron-energy-loss study) are proposed to be associated with edge and centre positions in very small c(2×2) domains as seen in a recent scanning tunnelling microscopy investigation.     

X-ray diffraction study of Si(111)√3 × √3-Au

The structure of the Si(111)√3 × √3-Au surface has been investigated by the use of the surface X-ray diffraction with synchrotron radiation. The structure perpendicular to the surface was determined with respect to the Si bulk crystal. The results of least-squares analysis indicate that Au atoms are adsorbed on the Si substrate in which the first Si layer is missing. The heights of the Au layer and the Si second layer with respect to the intact Si third layer were estimated to be 3.09 ± 0.03 rA and 2.16 ± 0.10 rA, respectively. A possible model of the surface structure is proposed.     

The role of van der Waals interaction in the tilted binding of amine molecules to the Au(111) surface

We present the results of ab initio electronic structure calculations for the adsorption characteristics of three amine molecules on Au(111), which show that the inclusion of van der Waals interactions between the isolated molecule and the surface leads in general to good agreement with experimental data on the binding energies. Each molecule, however, adsorbs with a small tilt angle (between -5 and 9°). For the specific case of 1,4-diaminobenzene (BDA) our calculations reproduce the larger tilt angle (close to 24°) measured by photoemission experiments, when intermolecular (van der Waals) interactions (for about 8% coverage) are included. These results point not only to the important contribution of van der Waals interactions to molecule-surface binding energy, but also that of intermolecular interactions, often considered secondary to that between the molecule and the surface, in determining the adsorption geometry and pattern formation.     

Comparative study of photochemistry of methane on Pt(111) and Pd(111) surfaces

Adsorption states and photochemistry of methane physisorbed on Pd(111) have been investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy and compared with those on Pt(111). On both of the surfaces, methane is either dissociated into a hydrogen atom and a methyl radical or molecularly desorbed by 6.4 eV photon irradiation. In the photochemistry, the direct electronic excitation of the adsorbate-substrate complex plays an important role. Different features observed for Pd(111) compared with Pt(111) are: (1) the adsorbate-substrate interaction is slightly stronger; (2) methane adsorbates show a (√3√3)R30° LEED pattern at 40 K; (3) the photochemical cross-section is larger by 60%; and (4) the photochemistry is not self-quenched at prolonged irradiation. The origins of these features are discussed in terms of the differences in the electronic structure between the two surfaces.     

Quantum-resolved angular distributions of neutral products in electron-stimulated processes: NO desorption from and NO2 dissociation on Pt(111)

We present the first quantum-resolved angular distributions of ground-state neutral molecules which are products of electron stimulated desorption (ESD) and electron stimulated dissociation. Laser resonance-enhanced multiphoton ionization (REMPI) and two-dimensional imaging have been used to obtain angular distributions of NO desorbed by 350 eV electrons from O-precovered Pt(111). In a similar fashion, we have measured angular distributions for the NO product of NO₂ dissociation on clean and O-precovered Pt(111). In all cases, we observe narrow widths which are roughly the same as ion distributions determined by ESDIAD (ESD ion angular distributions). The angular distribution for NO ESD is sharply peaked (7° half-width at half maximum) along the surface normal for an O coverage (θ_o) of 0.25 monolayer (ML). The angular distribution of the NO product from dissociation of side-bonded NO₂ on clean Pt(111) is unexpectedly peaked about the surface normal, and thus does not reflect dissociative forces parallel to the surface or the 25° off-normal ground-state bond direction. On O-precovered Pt(111), where NO₂ is N-bonded, 6° off-normal beams are observed. When the substrate is precovered with θ_o > 0.5 ML, local disorder creates asymmetric site geometries which result in multiple peaked angular distributions with both normal and off-normal (9–10°) components; similar effects for NO ESD are observed. In all these studies, the NO angular distributions are invariant to rotational or vibrational state. This implies that the lateral translational degrees of freedom are essentially de-coupled from the internal modes of the molecule. The results are discussed in terms of desorption mechanisms, dissociative forces, site geometries, and disordered coadsorbate layers.     

不同覆盖度下丙硫醇在Au(111)面吸附的理论研究

采用基于密度泛函理论的第一性原理方法研究了丙烷硫醇 (C₃H₇SH)在Au(111)面五种覆盖度(1/16, 2/16, 3/16, 4/16, 1/3) 下的未解离和解离吸附的结构、能量和吸附性质. 发现丙烷硫醇的倾斜角和吸附能均受覆盖度影响, 计算结果显示丙烷硫醇的倾斜角随着覆盖度的增大减小了6°–10°, 吸附能随覆盖度的增大减小了0.21 eV. 特别针对饱和覆盖度, 研究了三种可能的表面结构: (2√3×2√3 ight)R30°, 2√3×3和(3×3). 发现S–H键未解离时三种表面结构的吸附构型和吸附能基本一致; S–H键解离后, (2√3×2√3 ight)R30°和2√3×3结构的吸附能比以(3×3)结构的吸附能约高0.05–0.07 eV, 说明C₃H₇S在Au(111)面吸附时, 倾向于形成(2√3×2√3 ight)R30°和2√3×3结构. 此外, 采用DFT-D2方法对饱和覆盖度下C₃H₇SH分子在Au(111)面的吸附进行了范德华修正, 结果显示分子间相互作用使吸附物和Au表面的距离减小, 该相互作用对吸附能的修正值为0.53 eV, 修正后结果与实验结果接近. 关键词： 第一性原理 覆盖度 表面结构 范德华力