Ex situ STM imaging with atomic resolution of Ni(111) electrodes passivated in sulfuric acid

Scanning tunneling microscopy has been used to study in air Ni(111) electrodes passivated in 0.05M H₂SO₄ at + 650 mV/SHE. Before passivation, the Ni(111) single crystal surface has steps along the 〈1̄10〉 directions with terraces having a width of a few hundred nanometers. After passivation, a mosaic structure is formed with crystallites of 2 to 3 nm in size and strip-like features extended mainly along the [12̄1] direction whose width ranges from 2 to 3 nm and which appear to be locally tilted from 5 to 13°. Atomic resolution imaging has been achieved on both of these features. It reveals a corrugated lattice whose parameters are 0.30 ± 0.02 nm and 117 ± 3° in agreement with those of NiO(111). The crystallites have smooth step edges along [1̄01] and [011̄]. The STM imaging of the passive film as well as its mosaic structure are discussed.     

Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.     

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen

Photoelectron spectroscopic studies of the oxidation of Ni(111), Ni(100) and Ni(110) surfaces show that the oxidation process proceeds at 295 and 485 K in two distinct steps: a fast dissociative chemisorption of oxygen followed by oxide nucleation and lateral oxide growth to a limiting coverage of 3 NiO layers. The oxygen concentration in the 295 K saturated oxygen layer on Ni(111) was confirmed by ¹⁶O(d,p) ¹⁷O nuclear microanalysis. At 295 and 485 K the oxide growth rates are in the order Ni(110) > Ni(111) > Ni(100). At 77 K the oxygen uptake proceeds at the same rate on all three surfaces and shows a continually decreasing sticking coefficient to saturation at ~2.1 layers (based upon NiO). An O 1sb.e. = 529.7 eV is associated with NiO, and O ls b.e.'s of ~531.5 and 531.3 eV can be associated, respectively, with defect oxide (Ni₂O₃) or (in the presence of H₂O) with an NiO(H) species. The binding energies (Ni 2p, O 1s) of this NiO(H) species are similar to those for Ni(OH)₂. Defect oxides are produced by oxidation at 485 K, or by oxidation of damaged films (e.g. from Ar⁺ sputtering) and evaporated films. Wet oxidation (or exposure to air) of clean nickel surfaces and oxides, and exposure of thick oxide to hydrogen at high temperature results in an O 1s b.e. ~531.3 eV species. Nuclear microanalysis ²H(³He,p) ⁴He indicates the presence of protonated species in the latter samples. Oxidation at 77 K yields O 1s b.e.'s of 529.7 and ~531 eV; the nature of the high b.e. species is not known. Both clean and oxidised nickel surfaces show a low reactivity towards H₂O; clean nickel surfaces are ~10³ times less reactive to H₂O than to oxygen.     

Surface electronic structure of polar NiO(111) films

The surface and electronic structure of polar NiO(111) films with or without facets, prepared on a Mo(110) substrate, were in situ studied using various surface analytical techniques. A new surface state located at 0.8–1.8 eV measured by electron energy loss spectroscopy was observed on faceted NiO(111) films, which is originated from surface Ni vacancies. This surface state is decreased by annealing or deposition of Ni atoms. The experimental results indicate that the charge transfer occurs between surface and bulk of the faceted NiO(111) films. Present work provides a model surface with polarity and facets, which can be used for further investigation on chemical adsorption of atoms or molecules as well as selective reaction.     

Adsorption and electron properties of thin nickel films on W(110) surface

The evolution of the properties of ordered nickel films with thicknesses increasing from one to three atomic monolayers (ML) adsorbed on the W(110) single crystal surface is studied under ultrahigh vacuum conditions by the methods of reflection-absorption infrared spectroscopy (RAIRS) and ultraviolet photoelectron spectroscopy (UPS). The film structure corresponds to that of the Ni(111) single crystal face. The RAIRS technique is used to study the vibrational properties of the probing NO molecules adsorbed on the nickel films studied. In the course of the nickel film growth, whereby its thickness increases from 1 to 3 ML, both the vibrational and photoelectron spectra exhibit significant variation, which is indicative of a change in the adsorption and electron properties of the film. Stabilization of the IR and photoelectron spectra at a film thickness of 3 ML indicates that this thickness corresponds to the formation of the main adsorption and electron properties of the deposit. At the same time, the vibrational spectra of NO molecules adsorbed on a monoatomic nickel film exhibit features typical of adsorption on the W[110] surface of a massive tungsten crystal.     

The interaction of acetylene with Ni(111), chemisorbed oxygen on Ni(111), and NiO(111); the formation of CH species on chemically modified Ni(111) surfaces

Ultraviolet photoelectron spectroscopy, temperature programmed thermal desorption and low-energy electron diffraction have been used to study the interaction of acetylene with a clean Ni(111) surface, with a Ni(111) surface having co-adsorbed oxygen and with an epitaxially grown NiO(111) surface produced by room temperature oxidation ofNi(111). The adsorption of a (2 × 2) overiayer of π-bonded acetylene or oxygen on the Ni(111) surface markedly alters the subsequent interaction and reaction of the surface with incident acetylene. We find that in the presence of either a (2 × 2) overiayer of oxygen or π-bonded acetylene, a new more strongly bound hydrocarbon phase forms at room temperature. We identify this new phase from its ionization levels as a CH species, and for saturation coverages we find approximately twice as many of these species as the number of π-bonded acetylene molecules in the (2 × 2) structure. Preadsorption of oxygen limits the adsorption of π-bonded acetylene but does not affect the subsequent formation of this CH species. Exposure of acetylene to NiO at room temperature produces only CH species. Based upon these results we propose idealized models for the bonding geometry of π-bonded acetylene and CH species on the Ni(111) surface. The conditions for the formation of CH species and the significance of CH species to surface reactions on Ni are also discussed.     

Scanning kinetic spectroscopy (SKS): A new method for investigation of surface reaction processes

Multiple reaction pathways are available to a polyatomic molecule interacting with a solid surface. Delineation of exact temperature regions in which the various pathways are either active or inactive is accomplished using a new method, Scanning Kinetic Spectroscopy (SKS). SKS uses a calibrated and collimated beam of reactant molecules incident upon a clean single crystal surface in UHV. A multiplexed quadrupole mass spectrometer (QMS) is enclosed inside a differentially pumped random flux shield, in line of sight to the crystal surface. The crystal temperature is programmed with a linear ramp (dT/dt = 2K/s.) and reactant consumption, product evolution, and desorption of stable surface species are simultaneously measured in one experiment. SKS data are presented here which characterize the reactions of methanol with the single crystal surfaces Ni(111), Cu(111), and Cu(111) plus preadsorbed oxygen. Application of the SKS method as an efficient probe of surface reaction pathways is illustrated by the contrasting chemistry of these surfaces. The methanol plus Ni(111) system is examined in detail in order to relate the observed SKS features to specific molecular reaction pathways on the Ni(111) surface.     

Epitaxial growth and magnetic exchange anisotropy in Fe3O4<Emphasis Type="Bold">/NiO bilayers grown on MgO(001) and Al</Emphasis>2O3(0001)

Epitaxial Fe3O4/NiO bilayers were epitaxially grown on MgO(001) and Al2O3(0001) substrates to investigate the influence of the fully spin compensated (001) and the non-compensated (111) NiO interface planes between the ferromagnetic (F) and antiferromagnetic (AF) layers on the AF/F exchange coupling. Bilayers of different magnetite thicknesses and constant NiO thickness were investigated. The structural characterizations indicate a perfect epitaxy of the two layers for the both growth directions in the two Fe3O4/NiO/MgO(001) and NiO/Fe3O4/Al2O3(0001) systems. An epitaxial ferrimagnetic (Ni,Fe)Fe2O4 phase is observed at the AF/F interface when the NiO oxide is grown on the top of the Fe3O4 layer while a perfectly flat AF/F interface is observed in the Fe3O4/NiO/MgO(001) system exhibiting only a very slight interdiffusion. Magnetic measurements indicate a relative strong bias at 300 K for the bilayers grown on Al2O3(0001), which decreases with the inverse of the ferrimagnetic layer thickness as theoretically expected. On the contrary, a zero exchange biasing is observed at 300 K for the bilayers grown on MgO(001).     

The adsorption of CO,O2, and H2 on Pt: I. Thermal desorption spectroscopy studies

Thermal desorption spectroscopy (TDS) has been used to study the chemisorption of CO, O₂, and h₂ on Pt. It has been found that TDS is quite sensitive to local surface structure. Three single crystal and two polycrystalline Pt surfaces were studied. One single crystal was cut to expose the smooth, hexagonally close-packed plane of the fee Pt crystal (the (111) surface). The other two single crystals were cut to expose stepped surfaces consisting of smooth, hexagonally close-packed terraces six atoms wide separated by one atom high steps (the 6(111) × (100) and 6(111) × (111) surfaces). Only one predominant desorption state was observed for CO and H adsorbed on the smooth (111) single crystal surface, while two predominant desorption states were observed for these gases adsorbed on the stepped single crystal surfaces. The low temperature desorption states on the stepped surfaces are attributed to desorption from the terraces, while the high temperature desorption states are attributed to desorption from the steps. TDS of CO from the polycrystalline foils exhibited some desorption states which were similar to those observed on the stepped single crystal surfaces, indicating the presence of adsorption sites on the polycrystalline foils that were similar to the terrace and step sites on the stepped single crystals. In general, these results suggest a high density of defect sites on the polycrystalline foils which can not be attributed simply to adsorption at grain boundaries. Oxygen was found to adsorb well on the stepped single crystals and on the polycrystalline foils, but not on the smooth (111) single crystal, under the conditions of these experiments. This is attributed to a higher sticking probability for dissociative O₂ adsorption at steps or defects than on terraces.     

Thickness-dependent orientation evolution in nickel thin films grown on yttria-stabilized zirconia single crystals

Microstructure evolution along with crystallographic orientation change as a function of film thickness was investigated in Ni thin films grown on (100) yttria-stabilized zirconia (YSZ) single crystal substrates. Texture development with two different orientation relationships, OR1: Ni {111}//YSZ {100} and OR2: Ni {100}//YSZ {100}, cube on cube orientation were identified by X-ray diffraction and transmission electron microscopy depending on the film thickness. The observed orientation transition reveals the existence of a critical thickness (～320?nm) favoring two different orientations in sputtered Ni films on YSZ (100) substrate.     

The adsorption of N2: Chemisorbed on Ni(110) and physisorbed on Pd(111)

The bonding of molecular N₂ has been investigated with angle resolved photoelectron spectroscopy and inelastic electron scattering. The spectra obtained from N₂ chemisorbed onto a Ni(110) surface are compared to CO chemisorbed onto Ni(110) and to N₂ physisorbed onto Pd(111). The N₂ molecular axis was found to be normal to the crystal surface for the chemisorbed state on Ni(110) and random for the physisorbed state on Pd(111). The NN and NiN₂ stretching frequecies indicate that the N₂ molecule is terminally bonded to a single Ni atom on Ni(110). The binding energies of the two outer σ states and one π state of chemisorbed N₂ were measured, indicating that the bonding of N₂ to a metal surface is different than CO. Both σ states drop in energy compared to the π level due to the fact that both of them are involved in the N₂ substrate bond. The symmetry of the gas phase N₂ molecule is reduced upon adsorption. The consequences of this are seen in the dipole active NN vibrational mode, the large intensity of the Ni-N₂ vibrational mode and the coupling of the adsorbate 4σ(2σ_u) level to the final state resonance which is forbidden by symmetry in the gas phase. Many electron excitation satellite lines are observed in the valence spectra of both the chemisorbed and physisorbed N₂. The physisorbed satellite lines are nearly identical to those seen in gas phase N₂, while the chemisorbed N₂ spectra has new satellite structure, due to the interaction with the substrate.     

A quantitative ion-scattering study of the Ni(110) surface during the early stages of oxidation

The adsorption of oxygen on clean Ni(110) has been studied at room temperature and at 475 K by Rutherford backscattering, using the effects of channeling and blocking, and lowenergy electron diffraction. At both temperatures successive LEED structures are formed at low oxygen coverage (?0.5 monolayer). With increasing oxygen content stoichiometric NiO is formed on top of the Ni(110) surface, at room temperature as an amorphous layer and at 475 K as patches of crystalline oxide, oriented with the NiO(100) planes parallel to the Ni(110) surface plane. At 475 K the nickel atoms in the interface region between oxide and substrate are displaced over a thickness of less than 2 monolayers. Based on the measurement of the oxide composition as function of coverage we suggest a modification of the island growth model as proposed by Holloway and Hudson for the Ni(100) and (111) surfaces.     

A LEED/UPS study on the interaction of oxygen with a Ni(111) surface

Exposure of a Ni(111) surface to oxygen leads at first to the formation of a chemisorbed overlayer which is characterized by a 2 × 2-superstructure and a maximum in the photoemission spectrum (hv = 40.8 eV) centered at 5.6 eV below the Fermi level E_F. The emission from the Ni d-states is nearly unaffected at this stage of interaction. After high oxygen exposures the epitaxial growth of NiO can be identified from the LEED pattern. The corresponding photoelectron spectrum is strongly altered and exhibits close agreement with the transition energies as calculated by Messmer et al. for a NiO₆^10- -cluster.     

Structure and vibrations of CO adsorbed on the Ni(100)p(2 × 2)O and c(2 × 2)O surfaces

Chemisorption of CO on the Ni(100)p(2 × 2)O and c(2 × 2)O surfaces has been investigated by high-resolution electron energy loss spectroscopy (EELS) and low-energy electron diffraction (LEED). At 175 K CO adsorption on Ni(100)p(2 × 2)O saturates at about 1 L exposure in a structure interpreted to be Ni(100)p(2 × 2)O—p(2 × 2)CO. The CO layer is stable at 175 K but desorbs readily around 300 K. The EEL spectrum for p(2 × 2)CO shows vibrational losses at 46 meV and 245 meV interpreted to be due to excitations of the Ni-C and C-O stretching vibrations of CO molecules bridge bonded to two nearest neighbour Ni atoms. This interpretation is also supported by the LEED observations. For the preceeding dilute CO layer the vibrational loss spectrum reveals CO adsorption both to Ni bridge sites and hollow sites. At 175 K CO does only adsorb stationary on p(2 × 2)O defects in the Ni(100)c(2 × 2)O surface and not at all on epitaxially grown NiO(111) and (100) surfaces.     

Steady state shapes of periodic profiles on (110), (100), and (111) surfaces of nickel

Periodic surface profiles with amplitudes of ≦0.4 μm and periodicities of 4–20 μm were prepared on Ni(110), (100), and (111) single crystal surfaces. These crystals were annealed in ultra-high vacuum (UHV) at 1073–1327 K after they had been cleaned by Ar ion bombardment and investigated by Auger electron spectroscopy. The geometry of the profiles was studied in UHV by laser diffraction and outside the vacuum by interference microscopy. The profiles have sinusoidal shapes on Ni(110) but trapezoidal shapes on both the (100) and (111) surfaces. This type of faceting can be understood on the basis of the anisotropic surface energy of Ni, with cusps at the (100) and (111) orientations. Model calculations show in the case of anisotropic surface energy that periodic profiles develop facets which correspond to the low surface energy orientations (close-packed surfaces).     

The effects of temperature upon NiO formation and oxygen removal on Ni(110)

Oxygen chemisorption and NiO nucleation and growth on Ni(110) have been studied with low energy electron diffraction and Auger electron spectroscopy. Changes in the Auger peak energies and shapes were shown to occur only upon NiO formation. The effects of step-changes in temperature upon NiO nucleation and growth were studied and it was shown that temperature steps or annealing during the chemisorption regime did not significantly affect either chemisorption or NiO formation. During NiO growth, temperature steps to a higher temperature caused reduced growth rates, while steps to lower temperature caused increased growth rates. The reaction rate constant from the island growth model was calculated and shown to agree with literature data. The values obtained from temperature step measurements agreed within a factor of two with those obtained for reactions without temperature steps. Therefore, no systematic temperature effect upon the NiO nuclei density was observed for Ni(110). The activation energy for growth of NiO was found to be 5.5 kcal/mole. Dissolution of oxygen into bulk nickel was also studied and it was shown that bulk diffusion of oxygen in nickel was not rate controlling. Rather, surface phase transitions were observed which allowed incorporation of oxygen over the temperature range of 150°C to greater than 800°C, depending on the quantity of oxygen already incorporated.     

Surface Diffusion Induced Growth of Solid Solution over a Free Crystal Surface

It has been shown that interdiffusion along a free vicinal crystal surface can lead, at comparably low temperatures, to layered growth of solid solution over the surface without the involvement of bulk diffusion. The alloy concentration distribution along the surface, as well as the normal rate of solution growth has been calculated. The formation of a layer of the solid solution has been experimentally observed on a vicinal (111) surface of Ni single crystal as a result of surface interdiffusion between Ni and a thin film of Au deposited on a part of the Ni surface. The surface diffusion coefficients, as well as other parameters responsible for the exchange rate between the adatoms and kinks of elementary steps have been measured in the temperature range 550–700°C.     

Molecular dynamics study of the mechanical characteristics of Ni/Cu bilayer using nanoindentation

<正>In the present work,a three-dimensional molecular dynamics simulation is carried out to perform the nanoindentation experiment on Ni single crystal.The substrate indenter system is modeled using hybrid interatomic potentials including the many-body potential embedded atom method(EAM),and two-body morse potential.To simulate the indentation process,a spherical indenter(diameter = 80 A,1 A=0.1 nm) is chosen.The results show that the mechanical behaviour of a monolithic Ni is not affected by crystalline orientation.To elucidate the effect of a heterogeneous interface, three bilayer interface systems are constructed,namely Ni(100)/Cu(111),Ni(110)/Cu(111),and Ni(111)/Cu(111).The simulations along these systems clearly describe that mechanical behaviour directly depends on the lattice mismatch. The interface with the smaller mismatch between the specified crystal planes is proved to be harder and vice versa.To describe the relationship between film thickness and interface effect,we choose various values of film thickness ranging from 20 A to 50 A to perform the nanoindentation experiment.It is observed that the interface is significant only for the relatively small thickness of film and the separation between interface and the indenter tip.It is shown that with the increase in film thickness,the mechanical behaviour of the film shifts more toward that of monolithic material.     

镍单晶膜上氧化镍的配位生长取向关系

对在膜面为(110),(001)和(111)的镍单晶膜上生成的氧化镍取向进行了电子衍射分析,除在(111)和(001)镍膜上肯定了前人已发现的氧化镍与镍的平行取向关系外,还在(110)和(001)镍单晶膜上发现了(111)_NiO∥(001)_Ni,〈110〉_NiO∥〈110〉_Ni取向关系以及〈110〉_NiO∥〈110〉_Ni氧化镍纤维织构。在所有氧化镍与镍的取向关系中均有〈110