Oxygen adsorption on an alkali metal-covered Ni(100) surface

The oxygen chemisorption on an alkali (Na, K, Cs) covered Ni(100) surface and its initial oxidation were studied by Auger and electron energy loss spectroscopy (ELS). It was found that in the presence of an alkali metal, the sticking coefficient S remains unity up to a given oxygen coverage of θ_O^cwhose value depends on the alkali overlayer concentration and the ionicity of the Ni-alkali metal bond. At a given oxygen coverage, the line shapes of Auger and loss spectra are almost the same for alkali-covered and clean Ni(100), which suggests that alkali metals cause no change in the character of the Ni-O bond. The effect of alkali metals is associated with increasing electron charge in the surface region, which facilitates oxygen chemisorption. The enhanced surface oxygen concentration in the presence of an alkali metal results in the formation of an oxide phase at lower oxygen exposures than is the case of clean Ni surfaces.     

Untersuchung über den einfluss von adsorbierten gasen auf die elektronen-energieverlust-spektren einer Ni(110)-oberfläche

Electron energy loss spectra on a (110) nickel surface exhibit characteristic changes upon adsorption of H₂, CO and O₂. The clean surface shows only the surface and bulk plasmon losses at 8 eV and 18 eV respectively. Adsorption of CO produces two new loss peaks at 13.5 eV and 5.5 eV. Loss peaks due to hydrogen adsorption at 15 eV and 7.5 eV show a strong correlation with the well known adsorption characteristics of this system. The oxygen induced losses are different for chemisorbed O on Ni and NiO. In any case the chemisorption-induced losses are well established for primary energies below 120eV. In the loss spectra with higher excitation energies only a drastic decrease of the surface plasmon loss peak-height is visible. If the new losses can be attributed to one-electron excitations from molecular orbital levels due to the chemisorption bond, with assumptions of the final state of the excited electron a determination of the postition of these levels can be made. In case of CO and H₂ reasonable results are evaluated.     

Study of chemisorption on copper low-index and stepped surfaces

Adsorption of CHCl₃, O₂, and hydrocarbons has been studied on Cu(111) and stepped surfaces using LEED, AES, and UPS at room temperature. We find that ordered Cl overlayers form upon Cu(111), Cu[3(111) × (100)], and Cu[5(111) × (100)] surfaces upon exposure to CHCl₃. Exposure to O₂ results in rearrangement of the Cu[5(111) × (100)] surface to hill-and-valley regions with large (111) areas, whereas Cu[2(111) × (100)] is stable for the same exposure. The photoemission spectra show new energy levels due to C1 above and below the Cu d band region and a small splitting of the halogen p orbitals. Effects consistent with interaction with the Cu d band are observed. Similar effects are observed with oxygen adsorption. The initial rate of Cl or O₂ chemisorption as measured by photoemission is proportional to the density of steps on these surfaces. Apparently, structural effects play an important role in chemisorption on metals (such as copper) with low density of states at the Fermi energy.     

CO和O在无序二元合金NiCu表面上的化学吸附

本文用一维紧束缚模型和单电子化学吸附理论,在平均T矩阵近似下,研究了CO和O在无序二元合金Ni_xCu_1-x表面上的化学吸附特性,结果表明,CO和O在Ni_xCu_1-x表面上的化学吸附具有类似的性质,随合金中Ni浓度的增加,化学吸附能降低,化学吸附加强,Cu在NiCu合金表面的偏析在一定程度上减弱了CO和O在NiCu表面上的吸附。 关键词：     

Adsorption an Einkristall-Oberflächen von Cu/Ni-legierungen. I

The adsorption of O₂ and CO on the (110) face of a Cu/Ni alloy (55 at% Cu) has been studied by means of low energy electron diffraction (LEED), Auger electron spectroscopy, work function measurements, and flash desorption. A comparison with the behavior of Cu(110) and Ni(110) is made. It is shown that the height of an Auger peak is proportional to the surface concentration of the corresponding species and that the surface composition of the alloy is identical with the composition of the bulk. Adsorption of oxygen leads to the formation of an ordered 2 × 1 structure, as is the case for Cu(110) and Ni(110). Further exposure causes disordered adsorption in contrast to the pure components where c6 × 2 respectively 3 × 1 structures are formed. Oxygen increases the work function of Cu and Cu/Ni by about 0.25 eV whereas for Ni the increase is > 1 eV. CO is not irreversibly adsorbed on Cu at 25°C, but forms a stable 1 × 1 structure on Ni(110). With the alloy two ordered phases (2 × 1 and 2 × 2) are observed. The flash desorption spectrum shows three maxima which are similar to the binding states of CO on Ni(110) and Ni(100). The results are discussed in view of the electronic structure of Cu/Ni alloys and the parameters influencing the configuration of adsorbed particles.     

Lateral interactions in the thermal desorption of H2 from clean Cu/Ni(110) alloy surfaces

The adsorption of hydrogen on a clean Cu10%/Ni90% (110) alloy single crystal was studied using flash desorption spectroscopy (FDS), Auger electron spectroscopy (AES), and work function measurements. Surface compositions were varied from 100% Ni to 35% Ni. The hydrogen chemisorption on a-surface of 100% nickel revealed strong attractive interactions between the hydrogen atoms in accordance with previous work on Ni(100). Three desorption states (β₁, β₂ and α) appeared in the desorption spectra. The highest temperature (α) state was occupied only after the initial population of the β₂-state. As the amount of copper was increased in the nickel substrate, desorption from the higher energy binding α-state was reduced, indicating a decrease in the attractive interactions among hydrogen atoms. The hydrogen coverage at saturation was not affected by the addition of copper to the nickel substrate until the copper concentration was greater than 25% at which a sharp reduction in saturation coverage occurred. This phenomenon was apparently due to the adsorption of hydrogen on Ni atoms followed by occupation of NiNi and CuNi bridged adsorption sites, while occupation of CuCu sites was restricted due to an energy barrier to migration.     

Theoretical studies of CO/Ni(100): Geometry,vibrational frequencies and ionization potentials for the on-top site

The chemisorption of CO on the (100) surface of Ni has been studied using an Ni₁₄ cluster and generalized valence bond (GVB) methods. CO is found to bond perpendicular to the Ni surface with optimized NiC and CO bond distances of 1.94 and 1.15 Å, respectively. The calculated NiCO bond strength is 29.7 kcal (experimental values 30–32 kcal). Vibrational frequencies are calculated to be 401 cm^?1 for NiC stretch, 327 cm^?1 for NiCO bend, and 2129 cm^?1 for CO stretch. This decrease of the CO frequency by 71 cm^?1 from the free molecule value is consistent with experiment based on self-consistent calculations of the positive ion states. We propose a new explanation for the loss of one PES peak upon chemisorption.     

Nickel carbonyl adsorption on the Ni(111) surface

Overlayers formed by the adsorption of Ni(CO)₄ in CO on the Ni(111) surface at 100 K were characterized using high resolution electron energy loss spectroscopy and thermal desorption spectroscopy. At temperatures below 135 K, molecular nickel carbonyl adsorbs on the CO saturated Ni(111) surface as suggested by several observations. Vibrational transitions characteristic of molecular Ni(CO)₄ are dominant. The energy dependence of both the elastic and inelastic electron scattering cross sections are dramatically altered by Ni(CO)₄ adsorption. All of the mass spectrometer ionization fragments typical of molecular Ni(CO)₄ are observed in the narrow thermal desorption peak at 150 K. The inelastic scattering cross sections for both adsorbed nickel carbonyl and adsorbed CO on the Ni(111) surface suggest that a nonresonant dipole scattering mechanism is dominant.     

无序二元合金（NixCu1－x）不同解理面上O吸附对Cu偏析的影响

应用计算机编程构造出了存在和不存在表面偏析的无序二元合金Ni_xCu_1-x (x=0.4)(１００)表面及(１１０)表面的原子集团模型，然后按覆盖度θ=0.5，构造 出了O吸附后的原子集团模型，应用Recursion方法计算了O在Ni_xCu_{1-x(存在偏析和不存在偏析时)无序二元合金(１００)和(１１０)表面吸附的电子结构.由此 得出：1)O吸附使合金表面态密度峰降低，带宽加宽，并且表面Ni原子的d电子与吸附质O原 子的s，p电子的共价作用比Cu更强烈；2)O吸附在NixCu1-x(x=0.4) (１１０)表面比(１００)表面更稳定；3)O的吸附抑制了Cu在表面富集，且这种作用主要表 现在表面一层. 关键词： 化学吸附 表面偏析 Recursion方法 态密度}     

Local probing of the surface chemical bond using X-ray emission spectroscopy

2 and CO on Ni(100), benzene on Ni(100) and Cu(110), and glycine adsorbed on Cu(110). New types of molecular states are observed which are directly related to the surface chemical bond. The long-accepted Blyholder model which is based on a frontier orbital concept cannot explain our results for N₂ and CO chemisorption. We find it necessary to offer a new picture where changes in the whole molecular orbital framework have to be considered. We show that both π and σ type interactions are important in describing the bonding in benzene to metal surfaces. The future prospect is illustrated by the adsorption of the simplest amino acid, glycine, on Cu(110). The adsorbate has four different atomic centers where X-ray emission spectra are obtained, providing a unique view of the local electronic structure. Accepted: 6 March 1997     

Benzene adsorption on nickel (100) and (111) faces studied by leed and high resolution electron energy loss spectroscopy

Studies of benzene (C₆H₆ and C₆D₆) adsorption have been performed by high resolution electron energy loss spectroscopy (HRELS) and LEED experiments on nickel (100) and (111) single crystal faces at room temperature. Chemisorption induces ordered structures, c(4 × 4) on Ni(100) and (2√3 × 2√3)R30° on Ni(111), and typical energy loss spectra with 4 loss peaks accurately identified with the strongest infrared vibration bands of the gazeous molecules. Benzene chemisorption preserves the aromatic character of the molecule and involves respectively 8 nickel surface atoms on the (100) face and 12 on the (111) face by adsorbed molecule. The interaction takes place via the π electrons of the ring. Significant shifts of the CHτ bending and CH stretching vibrations show a weakening of the CH bonds due to the formation of the chemisorption bond and a coupling of H atoms with the nickel substrate.     

Vibrational EELS,XPS and UPS study of CO chemisorbed on Pt10Ni90(111): Evidence for the existence of different sites

CO adsorption on the (111) face of a Pt₁₀Ni₉₀ alloy single crystal has been investigated at room temperature by vibrational electron energy loss spectroscopy (EELS) and photoelectron spectroscopy (XPS and UPS). Two well separated CO stretching modes develop at 2070 and 1820 ± 10 cm^?1, with their intensities reaching 64 and 36% respectively of the total intensity at saturation coverage. They are attributed to CO adspecies in terminal and bridge bonded configuration respectively. The UPS spectra of 4σ, 5σ and 1π molecular orbitais of adsorbed CO show complex features which may be resolved into two components having the main characteristics of CO adsorbed on pure Pt(111) and Ni(111) respectively. Such behaviour is also observed by XPS on C 1s on O 1s peaks. Their respective contributions, in both XPS and UPS spectra are about 64 and 36% of the whole spectrum. Finally compared to Ni(111) — on which CO adsorbs mainly in bridge configuration — the alloying with 10% Pt has generated the appearance of a large number of new sites for CO chemisorption associated with the presence of Pt atoms at the surface. The large amount of terminal CO adspecies is interpreted in terms of considerable surface enrichment of the alloy in platinum.     

Influence of film morphology on thin film ferromagnetism

Cobalt, nickel and their alloy, Co₁Ni₉, films were epitaxially grown on Cu(100) under different growth conditions and subsequent treatments and studied using surface magneto-optic Kerr effect (SMOKE) in an attempt to understand the effects of film morphology on the magnetic properties. CO contamination can significantly reduce the magnetization and Curie temperature. Thermal desorption spectroscopy (TDS) shows that CO desorbs at 422 K from Ni and 410 K from Co₁Ni₉ at a heating rate of 6 K per minute. Annealing the films below 450 K produces smooth and clean films with stable magnetic behavior. However, annealing at higher temperatures results in Cu segregation and island formation leading to the finite-size ferromagnetic or even superparamagnetic behavior.     

LEED and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 and C) chemisorbed on the stepped rhodium (755) and (331) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₂, C₂H₄ and C has been studied on the clean stepped Rh(755) and (331) surfaces. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) were used to determine the size and orientation of the unit cells, desorption temperatures and decomposition characteristics for each adsorbate. All of the molecules studied readily chemisorbed on both stepped surfaces and several ordered surface structures were observed. The LEED patterns seen on the (755) surface were due to the formation of surface structures on the (111) terraces, while on the (331) surface the step periodicity played an important role in the determination of the unit cells of the observed structures. When heated in O₂ or C₂H₄ the (331) surface was more stable than the (755) surface which readily formed (111) and (100) facets. In the CO and CO₂ TDS spectra a peak due to dissociated CO was observed on both surfaces. NO adsorption was dissociative at low exposures and associative at high exposures. C₂H₄ and C₂H₂ had similar adsorption and desorption properties and it is likely that the same adsorbed species was formed by both molecules.     

Molecular cluster theory of CO chemisorption on a nickel(100) surface

Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of carbon monoxide on a (100) transition metal surface are presented. Energy levels and charge distribution for the CO: Ni₅ cluster in C_4v symmetry are obtained, and the variation of binding energies with height of the CO molecule above the surface of nickel is studied in detail. Comparison is made with experimental binding energy spectra and with the multiple-scattering results of Batra and Bagus. The redistribution in energy of free-atom valence levels is studied by means of local-densities-of-states diagrams.     

Low temperature electron energy loss spectra of acetylene chemisorbed on metal single-crystal surfaces; Cu(111), Ni(110) and Pd(110)

Vibrational spectra of acetylene chemisorbed on Cu(111), Ni(110) and Pd(110) at 110–120 K were measured using electron energy loss spectroscopy. Loss peaks were assigned to vibrational modes of the non-dissociatively adsorbed molecules with the aid of the corresponding C₂D₂ spectra. The spectra show that the molecules undergo significant rehybridisation on adsorption. Comparisons are made with the spectra of acetylene adsorbed on a range of other transition metal surfaces at low temperature. Taking into account these and earlier literature results, two distinct patterns of spectra are observed (Type A and Type B) for specular spectra. The Cu(111) spectrum is classified as Type A while the Ni(110) and Pd(110) spectra are classified as Type B. Suggestions are made for the structures of the surface species corresponding to the two spectral types.     

Initial oxidation of the Mg(0001) surface,an electron spectroscopy study

The initial oxidation of Mg(0001) has been studied using AES (Auger electron spectroscopy), LEED (low energy electron diffraction), and EELS (electron energy loss spectroscopy). The oxidation proceeds through different stages; first oxygen atoms are incorporated to chemisorption sites below the top layer magnesium. This chemisorption phase is followed by the formation of an oxide layer. The oxide layer covers the Mg surface after an oxygen exposure of ～ 10 L O₂. After this exposure the bulk-like MgO formation slowly increases the oxide thickness. The oxide layer formed for exposures up to ≤ 10 L O₂ gives rise to a diffuse LEED pattern of the same symmetry as the original “clean” LEED pattern; the possibility of an epitaxial oxide formation at this stage is discussed.     

Characterization of the adsorption and decomposition of methanol on Ni(110)

The chemisorption, condensation, desorption, and decomposition of methanol, both CH₃OH and CH₃OD, on a clean Ni(110) surface have been characterized using high resolution electron energy loss spectroscopy, temperature programmed reaction spectroscopy, and low energy electron diffraction. The vibrational spectrum of the saturated chemisorbed layer, 7.4 × 10¹⁴ molecules cm^?2, is almost identical to the infrared spectrum of liquid or solid methanol. Condensation of multilayers of methanol is facile at 80 K. The only quasi-stable intermediate isolated during the decomposition is a methoxy species, CH₃O, which decomposes thermally to CO and H. The evolution of both CO and H₂ occurs in desorption limited processes.     

Cathodoluminescence of copper and nickel surfaces

Cathodoluminescence spectra of clean and oxidized Cu(100) and Ni(100) surfaces, using 60–1000 eV electron bombardment, has been measured. A broad peak at 310 nm has been observed for both clean Cu and Ni surfaces. This peak is attributed to radiative recombination of electrons from the point X'₄ with holes at the point X₅ of the energy band diagram. A narrow peak at 520 nm has been found to correlate with the growth of oxide on the Cu and Ni surfaces. This peak can be attributed to electronic transitions involving energy levels of the O^2- ions. The cathodoluminescence technique appears useful for studying the initial growth of metal oxides.     

Direct production of carbon nanotubes decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Carbon nanotubes (CNTs) decorated with Cu₂O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 45 °C using the corrosive effect of H₂SO₄ which was added to solution. These nanoparticles provide the nucleation sites for CNT growth avoiding the need for a buffer layer. The surface morphology of the Ni catalyst films and CNT growth over this catalyst was studied by scanning electron microscopy (SEM). High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O₂ at atmospheric environment, during the CNTs growth, lead to the production of CNTs decorated with about 6 nm Cu₂O nanoparticles. We used SEM to study the surface characteristics of Ni catalyst films and characteristic of grown CNTs. Raman spectroscopy, transmission electron microscopy (TEM), electron diffraction (EDX), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) revealed the formation of CNTs. The selected area electron diffraction pattern, EDX, and XPS studies show that these CNTs were decorated with Cu₂O nanoparticles. This way of fabrication is the easiest and lowest cost method.