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.     

Adsorption and reaction of oxygen and deuterium on a Pd(110) surface, studied by Δφ and TDS

The co-adsorption of oxygen and deuterium at 100 K on a Pd(110) surface has been studied by measurements of the change in work function (Δφ) and by thermal desorption spectroscopy (TDS). When the surface with co-adsorbed species is heated, the adsorbates O and D react to form D₂O which desorbs from the surface at T > 200 K. The D₂O desorption peaks shift continuously to lower temperatures as the surface D coverage (θ_D) increases. The maximum production of D₂O is estimated to be 0.26 ML (1 ML = 9.5 × 10¹⁴ atoms cm⁻²), resulting from reaction in a layer containing 0.65 ML D and 0.3 ML O. The maximum work function increase caused by adsorption of D to saturation onto oxygen precovered Pd(110) decreases almost linearly with Δφ_O of the oxygen precovered surface. On a surface with pre-adsorbed D however, the maximum Δφ increase contributed by oxygen adsorption decreases abruptly at Δφ_D > 200 mV. This sharp change occurs at θ_D > 1 ML and is believed to be associated with the development of the reconstructed (1 × 2) phase of D/Pd(110).     

Coadsorption of water and CO molecules on Ru(0 0 1) at high CO coverages: comparisons with a Ru(0 0 1) electrode surface

The coadsorption of carbon monoxide (CO) and water molecules on a Ru(0 0 1) surface has been studied by infrared spectroscopy, LEED and STM. At high CO coverage phases, a 2×2-(2CO+D₂O) structure was observed on both UHV and electrode surfaces. Electrode potential dependent structures from CO and water adlayers on an electrode surface were reproduced on a UHV surface by controlling molecular orientations of the first layer and second over-layer water molecules. At lower CO coverages, a CO band center showed coverage dependent shift down to 1444 cm⁻¹ due to an electron transfer from a lone pair of a water molecule to CO 2π^*.     

Hydrogen induced structure changes of GaAs(1 0 0) surfaces

The interaction of hydrogen with GaAs(1 0 0) surfaces has been studied at room temperature by means of high-resolution electron energy-loss spectroscopy (HREELS), low-energy electron-diffraction (LEED), and Auger electron spectroscopy (AES). Sample cleaning by Ne⁺ ion bombardment (500 eV) and annealing resulted (with increasing temperatures) in “1 × 1”, 1 × 6, 4 × 1, 4 × 6 and c(8 × 2) LEED structures. As a function of hydrogen exposure, the intensity ratio of the stretching vibrations (As-H/Ga-H) is shown to be characteristic for the specific reconstructed surface. In particular the arsenic hydride concentration gradually decreased in all cases. In addition, an initial weakening of the fractional order LEED spots occurred with increasing hydrogen exposures. Finally, a strong 1 × 2 structure was observed independent of the reconstruction we started with. Simultaneously, a shift of the energetic position of the Ga-H stretching vibration occurred.     

The interaction of D2O with Zr(0001) at 80 K

The adsorption of D₂O on Zr(0001) at 80 K and its subsequent reactions at higher temperatures have been studied by thermal desorption spectroscopy (TDS), work-function measurements (Δф), nuclear reaction analysis (NRA), LEED, infrared reflection spectroscopy (FTIR-RAS), Auger electron spectroscopy (AES), and static secondary ion mass spectroscopy (SSIMS). D₂O adsorption on Zr(0001) at 80 K is accompanied by a Δф of −1.33 eV. The adsorbed D₂O can be characterized into three layers by TDS: a chemisorbed layer (up to 0.23 ML), a second adsorbed layer, and an ice layer. The chemisorbed D₂O dissociates into OD_ad and D_ad at 80 K (possibly also into O_ad) and no desorption products could be detected, implying that the reaction products dissolved into the zirconium at temperatures appropriate for each component. The ice layer and most of the second adsorbed layer desorb as molecular water during heating. The water adsorbed at 80 K did not form any long-range ordered structure, but a (2 × 2) LEED pattern that was formed by heating the sample to temperatures above 430 K is believed due to be an ordered oxygen superstructure.     

Vibrational spectroscopy of ordered oxygen adiayers on Ni/Cu(001) and Co/Cu(001) thin film systems

We report surface vibrations in c(2 × 2) oxygen adlayers on Ni and Co thin films on a Cu(001) substrate measured at gG by high resolution EELS. For the Ni thin film surface, one phonon peak is measured for varying film thicknesses from 1.3 ML (monolayer) to 6 ML with a constant energy of 221 cm⁻¹. For the Co thin film surface, three loss peaks are found, whose relative intensities change as the film thicknesses are varied. One loss peak at ˜520 cm⁻¹ is tentatively assigned to the Fuchs-Kliewer mode of cobalt oxide (CoO). The other two peaks at 317 and 376 cm⁻¹ are likely related to different bonding sites. Surface phonons on the p(2 × 2) Co thin film (389 cm⁻¹) and a bulk resonance mode (115 cm⁻¹) are also reported.     

The adsorbate-induced removal of the Pt{100} surface reconstruction Part I: NO

The molecular adsorption of NO on both the reconstructed (hex) and unreconstructed (1 × 1) surfaces of Pt{100} has been studied using a combination of infrared reflection-absorption spectroscopy (IRAS) and low energy electron diffraction (LEED) at temperatures between 90 and 300 K. On the (1 × 1) surface at 300 K adsorbed NO gives rise to an N-O stretching band at initially 1596 cm⁻¹ shifting to 1641 cm⁻¹ at a coverage of θ = 0.5. The LEED pattern at this coverage is interpreted in terms of a c(4 × 2) structure in which all the molecules occupy a single type of adsorption site between the on-top and bridge positions. At temperatures below 300 K, a higher coverage disordered phase is observed, giving rise to an N-O stretching band at 1680 cm⁻¹ associated with an on-top NO species. On the (hex) phase surface above 210 K, NO adsorption gives rise to bands characteristic of adsorption on the (1 × 1) phase indicating that the reconstruction is immediately lifted. Below 200 K initial adsorption actually occurs directly on the (hex) phase, resulting in a band at 1680 cm⁻¹, which is assigned to on-top NO. This band increases in intensity until, at a critical coverage dependent on temperature, the (hex) → (1 × 1) surface phase transition is induced. This is indicated by the disappearance of the band at 1680 cm⁻¹ and its replacement by bands characteristic of adsorption on islands of the (1 × 1) structure.     

Dynamic observations of the formation of thin Cu layers on clean and hydrogen-terminated Si(1 1 1) surfaces

The growth of Cu on the clean and hydrogen-terminated Si(1 1 1) surfaces is studied in situ by low-energy electron microscopy (LEEM). The dependence of the growth of the “5×5” layer on the clean Si(1 1 1) 7×7 surface upon the deposition temperature is investigated by combining LEEM with LEED. After completion of the “5×5” layer not only the regular-shaped three-dimensional islands reported before are observed but also irregular shaped more two-dimensional islands. On the hydrogen-terminated Si(1 1 1) surface the formation of the “5×5” structure is suppressed and nano-scale islands form preferentially at the step edges and domain boundaries. This is attributed to the enhancement of the surface migration of Cu atoms by the elimination of the surface dangling bonds.     

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.     

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.     

ESDIAD studies of the structure of TiO2(110)(1 × 1) and (1 × 2) surfaces and interfaces in conjunction with LEED and STM

The TiO₂(110)-(1 × 1) surface and its reconstruction as a (1 × 2) form have been studied with low energy electron diffraction (LEED), electron stimulated desorption ion angular distribution (ESDIAD) and scanning tunnelling microscopy (STM). Oxygen ion desorption occurs within a lobe perpendicular to the (1 × 1) surface, changing to two off-normal lobes for the (1 × 2) reconstruction. This transformation in the ESDIAD pattern is consistent with the added Ti₂O₃ row model of the (1 × 2) reconstruction proposed by Onishi and Iwasawa. STM studies of the stoichiometric and electron irradiated surfaces reinforce the association of the O⁺ ESD contribution with majority sites at the surface. Adsorption of acetic acid on the (1 × 1) surface produces a (2 × 1) overlayed and induces a reconstruction of the underlying substrate. ESDIAD reveals H⁺ ions emitted off-normally from dissociatively adsorbed acetate, and along the surface normal from surface hydroxyls. Adsorption of acetic acid on the (1 × 2) surface does not modify the LEED pattern, but ESDIAD reveals H⁺ desorption with a weaker off-normal contribution consistent with the Ti₂O₃ model of the reconstruction.     

STM investigations of CO coadsorption with O and with S on Ni(110)

The interaction between CO coadsorbed with oxygen and sulfur on Ni (110) has been studied with room temperature STM and LEED. In the case of CO/O/Ni(110)−(θ_o0.3 ML), it is found that due to a large local repulsion between the differing species, the coadsorbed species phase separate into large domains of O−(3 × 1) and CO−p2mg(2 × 1) structure. Similarly in the case of CO/S/Ni(110)−(θ_s0.4 ML), at low local coverages of coadsorbed CO, island segregation of CO and S-c(2 × 2) is observed. At locally saturated CO coverage, the S-c(2 × 2) structure transforms into long -S-S- chains running predominantly along the [ ] direction and separated by a local p2mg(2 × 1)-CO structure; this transformation is attributed to the large CO-CO repulsion in the condensed overlayer structure.     

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.     

The interaction of hydrogen with polycrystalline zirconium I. Sticking coefficients and binding states

Values for the sticking coefficient of hydrogen on polycrystalline zirconium have been obtained using a computer-controlled flash desorption technique. Sticking coefficients exhibit a maximum of about 6.5 × 10^-4 near 700 K and fall to about 4 × 10^-5 below 350 K and above 1000 K. Such low values are surprising in view of the well-known effectiveness of zirconium as a “getter” material for hydrogen. Plots of desorption rate versus temperature show two binding states below the phase transition temperature and at least one (and possibly two) above that temperature.     

Sodium adsorption on a Ge(100)-(2 × 1) surface

The adsorption of Na on a Ge(100)-(2 × 1) surface has been studied by means of AES, LEED, EELS, TPD and work-function measurements. In the submonolayer coverage region the coverage dependencies of the desorption activation energy E(Θ) and desorption frequency v(Θ) have been determined using the threshold TPD method. Our experimental data show that after the completion of the first Na layer, 3D crystallites develop on the Na/Ge(100) surface (Stranski-Krastanov growth mode). For Θ > 1 ML, formation, followed by decomposition of a certain Na---Ge surface compound occurs in the temperature range 410–550 K.     

Hydrogen adsorption on Mo1−xRex(110) (x=0–0.25) surfaces

The effects of adsorbed H on the Mo_1−xRe_x(110), x=0, 0.05, 0.15, and 0.25, surfaces have been investigated using low-energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS). For the x=0.15 alloy only, a c(2×2) LEED pattern is observed at a coverage Θ0.25 ML. A (2×2) pattern is observed for H coverages around Θ0.5 ML from surfaces with x=0, 0.05, and 0.15. Both c(2×2) and (2×2) patterns are attributed to reconstruction of the substrate. At higher coverages, a (1×1) pattern is observed. For the alloy surface with x=0.25, only a (1×1) pattern is obtained for all H coverages. Two H vibrations are observed in HREELS spectra for all Re concentrations, which shift to higher energies at intermediate coverages. Both peaks exhibit an isotopic shift, confirming their assignment to hydrogen. For Re concentrations of x=0.15 and higher, a third HREELS peak appears at 50 meV as H (D) coverage approaches saturation. This peak does not shift in energy with isotopic substitution, yet cannot be explained by contamination. The intrinsic width of the loss peaks depends on the Re concentration in the surface region and becomes broader with increasing x. This broadening can be attributed to surface inhomogeneity, but may also reflect increased delocalization of the adsorbed hydrogen atom.     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.     

The reaction of H2S with surface oxygen on Ni(110)

The reactions of H₂S with predosed surface oxygen on Ni(110) surfaces were studied for a variety of coverage conditions. The primary reaction product is H₂O, but the details of the water formation and desorption depends on the coverage of both O and H₂S.

For high coverages of oxygen (p(2 × 1)−O; 0.5 ML), the reaction to form water is quantitative. The loss of oxygen from the surface (as measured by AES) is equal to the increase in sulfur coverage. XPS and HREELS measurements indicate the presence of chemisorbed H₂O immediately following large exposures of H₂S on the oxygen predosed surface at 110 K. Deuterium incorporation results suggest that the primary mechanism for these coverage conditions involves direct transfer of hydrogen from SH or H₂S moieties to the oxygen.

A second mechanism involving reaction of surface hydroxyl groups with surface hydrogen was also identified. This mechanism is particularly important for high coverages of oxygen (0.5 ML) and low coverages of H₂S (0.15 ML), where water desorption was observed at 235 K, but was not observed spectroscopically at 110 K. The sequential addition of two surface hydrogen atoms to surface oxygen is not an important mechanism in this system.

These reactions were modeled using a bond-order conservation method, and the model successfully reproduced the important mechanistic conclusions.     

Structure of the Si(011)-(16 × 2) surface and hydrogen desorption kinetics investigated using temperature-programmed desorption

D₂ temperature-programmed desorption (TPD) was used to probe the structure of the Si(011)-(16 × 2) surface. Deuterium was adsorbed at 200°C to coverages θ_D ranging up to complete saturation (approximately 1.1 ML) and the sample heated at 5°C s⁻¹. TPD spectra exhibited three second-order desorption peaks labelled β₂, β*₁ and β₁ centered at 430, 520 and 550°C. Of the proposed models for the Si(011)-(16 × 2) reconstruction, the present TPD results as a function of θ_D provide support for the adatom/dimer model with the β₂ peak assigned to D₂ desorption from the dihydride phase, while the β*₁ and β₁ peaks arise from adatom and surface-atom monohydride phases.     

Escape of charged particles at stopping annihilation of antiprotons in the heavy nuclei of nuclear photoemulsion

“Rare” annihilation channels for antiprotons stopping on heavy (Ag, Br) nuclei of photoemulsion, have been sought; 4872 stops of antiprotons on photoemulsion nuclei are analysed. Events of formation and decay of the hyperfragment _Λ⁴H, escape of ⁸He and ⁸Li nuclei, one-prong stars with the mean range 79.5±5.1 μm of secondary slow “b” particles are found among the annihilation stars at capture on nuclei (Ag, Br). The lower limits for the production probability of _Λ⁴H and ⁸He, ⁸Li nuclei per antiproton stopping in the nuclei (Ag, Br) are

W_Λ⁴H2×10⁻⁴ and W_⁸He,⁸Li=(1.3±0.6)×10⁻³.

The branching ratio for the production of one-prong stars with the secondary “b” particles is at least (1.3±0.6)×10⁻³. Possible mechanisms for a production of these events in annihilation processes are considered.