Monolayer structure of phenoxy species on Cu(110): an STM study

The monolayer structure of phenoxy species (PhO) on a metal surface has been studied for the first time with scanning tunneling microscopy (STM). The phenoxy species was produced by exposing the Cu(110) surface to phenol at room temperature. The monolayer exhibits a c(4 × 2) LEED pattern; however, molecular resolution STM imaging of the monolayer reveals three types of overlayer structures: (1) a densely packed c(4 × 2) or 4002 structure with a coverage of 0.25 PhO per surface copper atom, (2) more densely packed phenoxy chains separating the c(4 × 2) regions with a local coverage of 0.33 PhO per Cu, and (3) a distorted c(4 × 2) or 4102 structure consisting of phenoxy chains. Structural models are proposed for each case based on the real dimensions measured with STM. These structures exhibit a constant binding site for the phenoxy species with different orientations (from nearly parallel to almost normal) with respect to the surface plane. The “15°–20° tilts” measured by other techniques on Pd(110) and Ni(110) may be affected by the sum of different structures.     

Carbidic carbon on Ni(110): an STM study

The interaction of carbon with the Ni(110) surface has been investigated by scanning tunneling microscopy (STM). Dissociation of ethylene at elevated temperatures resulted in the formation of two carbidic carbon structures, (4 × 3) and (4 × 5), both of which are formed by a significant reconstruction of the surface involving a long-range mass transport of 0.5 ML Ni. The density of C in the reconstructed phases was estimated based on Auger electron spectroscopy (AES). Atomic models, which are consistent with all existing experimental observations for carbidic carbon on Ni(110), are proposed for the (4 × 3) and (4 × 5) phases.     

Atomic adsorption of oxygen on Cu(111) and Cu(110)

We have studied angle-resolved inverse photoemission ( = 9.7 eV) after room temperature adsorption of oxygen on Cu(111) and Cu(110). On Cu(111) exposure to 500 L induces a band (3.0 eV aboveE _F at) which shows clear dispersion (1.0 eV) to higher energies for off normal incidence. Since no LEED superstructure is seen for that system, our results present strong evidence for the presence of short-range surface order. Two adsorbate bands are identified (2.8 eV and 6.3 eV at) on Cu(110)p(2×1)-O. Our results are in good agreement with a long-bridge adsorption site.     

STM studies on the growth of monolayers: Co on Cu(110) with one half monolayer of preadsorbed oxygen

The growth of the first cobalt monolayer (ML) on the Cu(110)-(2×1)O surface was studied by scanning tunneling microscopy. Extensive exchange of Cu and Co atoms takes place in the first stages of the deposition. The displaced Cu atoms form new Cu---O---Co mixed islands, with the same structure as those of the terrace surface. At 0.25 ML Co, a new structure nucleates, which contains three Cu atoms, four Co atoms and two O atoms per 2×2 cell. The structure consists of rows in the [ 10] direction with an internal periodicity of two lattice units. The rows are separated from one another by two lattice units along the [001] direction, and are found both in-phase and out-of-phase relative to one another. The result is a mixed p(2×2) and c(2×4) surface. The fraction of the surface covered by the new structure increases with Co coverage, and completely covers the surface at 1 ML Co.     

Growth of 3,4,9,10-perylenetetracarboxylic-dianhydride (PTCDA) on Cu(110) studied by STM

. The structure of thin 3,4,9,10-perylenetetracarb-oxylic-dianhydride (PTCDA) films on Cu(110) was studied by scanning tunnelling microscopy (STM) from submonolayer to monolayer coverage. While no long-range ordering was found after deposition at room temperature, the formation of a well-defined superstructure is observed after thermal annealing. It appears that the formation of the superstructure is driven by the interaction between the oxygen atoms of the PTCDA and the copper atoms of the substrate. While the distance between the molecules fits well to the atomic lattice of the Cu(110) surface along the [1[`(^[¯])]1^[¯]\bar\Box1\Box]]0] direction, the mismatch along the [001] direction leads to a periodic buckling normal to the surface accompanied by a restructuring of the substrate.     

Vacancy diffusion in the Cu(001) surface I: an STM study

We have used the indium/copper surface alloy to study the dynamics of surface vacancies on the Cu(0 0 1) surface. Individual indium atoms that are embedded within the first layer of the crystal, are used as probes to detect the rapid diffusion of surface vacancies. STM measurements show that these indium atoms make multi-lattice-spacing jumps separated by long time intervals. Temperature dependent waiting time distributions show that the creation and diffusion of thermal vacancies form an Arrhenius type process with individual long jumps being caused by one vacancy only. The length of the long jumps is shown to depend on the specific location of the indium atom and is directly related to the lifetime of vacancies at these sites on the surface. This observation is used to expose the role of step edges as emitting and absorbing boundaries for vacancies.     

XPS and STM study of carbon deposits at the surface of platinum (110)

The deposition of carbon due to high temperature ethylene decomposition at Pt(110) was studied by XPS and STM techniques. In the temperature range 700–1400 K no graphite species were observed. Instead, two carbon states were distinguished by XPS. At temperatures 700–850 K chemisorbed carbon layer is formed with BE(C1s) = 284.2 eV, this carbon state reacting readily with both oxygen and hydrogen. At T> 850 K carbon layer with BE(C1s) = 284.6–284.9 eV is formed. Further study showed this carbon species to be stable up to 1150 K and to be inert towards both hydrogen and oxygen up to 1000 K. This state was attributed to diamond-like carbon (DLC). STM study of DLC on Pt(110) revealed the patched pseudo-C-(3 × 1) structure. This reconstruction is believed to account for the DLC formation at platinum (110) surface.     

Dissociative and molecular oxygen chemisorption channels on reduced rutile TiO2(110): An STM and TPD study

High-resolution scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) were used to study the interaction of O₂ with reduced TiO₂(110)–(1 × 1) crystals. STM is the technique of choice to unravel the relation between vacancy and non-vacancy assisted O₂ dissociation channels as a function of temperature. It is revealed that the vacancy-assisted, first O₂ dissociation channel is preferred at low temperature (~ 120 K), whereas the non-vacancy assisted, second O₂ dissociation channel operates at temperatures higher than 150 K–180 K. Based on the STM results on the two dissociative O₂ interaction channels and the TPD data, a new comprehensive model of the O₂ chemisorption on reduced TiO₂(110) is proposed. The model explains the relations between the two dissociative and the molecular O₂ interaction channels. The experimental data are interpreted by considering the available charge in the near-surface region of reduced TiO₂(110) crystals, the kinetics of the two O₂ dissociation channels as well as the kinetics of the diffusion and reaction of Ti interstitials.     

NiTi(110)表面氧原子吸附的第一性原理研究

为了研究给定的NiTi的表面氧化过程,在保持体系中Ni和Ti原子总数相等的条件下,构建了一系列Ti原子在表面反位的c(2×2)-NiTi(110)缺陷体系,并利用第一性原理计算研究了氧原子在各种NiTi(110)反位缺陷体系的吸附行为以及表面形成能.计算结果表明:吸附氧原子的稳定性与表面Ti原子的富集程度有很大的关联性,体系表面Ti原子富集程度越高,氧原子吸附的稳定性越高;当覆盖度较高时,由于氧原子的吸附,可使Ni和Ti原子在表面出现反位.在富氧条件(μ_o≥-9.35 eV)下,氧原子在表面第1层中的全部Ni原子与第3层全部Ti换位的反位缺陷体系上的吸附最稳定,此时随着氧原子的吸附,表面上的Ti原子升高,导致向上膨胀生长形成二氧化钛层,且在其下方形成富Ni层,由此可合理地解释实验上发现NiTi合金氧化形成二氧化钛层的可能原因.     

Initial growth of Cu films on oxygen covered W(110)

The growth of Cu films on the p(2 × 1)O-W(110) and (1 × 1)O-W(110) surfaces has been monitored using specular He scattering. Deposition at temperatures below 200 K leads to rough films on both surfaces. Deposition at T > 300 K leads to phase separation of Cu and O on the p(2 × 1)O-W(110) surface. Deposition at 300 K on the higher oxygen coverage surface leads to films which are nearly as smooth as these deposited on clean W(110). Deposition at 800 K leads to needle-like crystallite formation without an initial continuous film.     

Intermediate product identification for ammonia decomposition at Ni (110)

Ammonia decomposition at Ni(110) has been identified to proceed via NH₃(ad) → NH₂(ad) → NH(ad) → N + H. The decomposition activation of NH is determined to be 47 kcal/mol, suggesting an amazing stability of the NiNH bond. Decomposition of NH₂ occurs up from about 350 K; no kinetic data can be given yet. NH₃ decomposition is found to proceed slower than NH₃ desorption at least below 300 K.     

Electronic excitations at oxygen deficient TiO2(110) surfaces: A study by EELS

TiO₂(110) surfaces with controlled oxygen deficiency introduced by 160 eV electron bombardment have been studied by XPS and EELS. Stoichiometry was monitored by the growth of core peaks due to Ti³⁺ states in XPS. Oxygen desorption is characterised by an initial cross section of 3 × 10⁻²¹ cm² that decreases with increasing oxygen loss, tending toward a limiting composition Ti₄O₇. The oxygen deficient surfaces display sub-bandgap excitations in electronic EELS, whilst in the vibrational region there is a selective downward shift and attenuation of the highest energy phonon loss. This is attributed to modification of the effective background dielectric constant by the defect excitations. Quantitative consideration of the changes in HREELS leads to an estimate of 0.1 for the oscillator strength of the defect electronic excitations. The high value supports the idea that electrons at oxygen deficient TiO₂ surfaces occupy states that are pulled down below the conduction band by polaronic self trapping.     

An adsorption-desorption study of Cu on Mo(110)

Thermal desorption spectroscopy (TDS), adsorption-desorption equilibrium (ADE), adsorption transient (AT) and desorption transient (DT) measurements are used to study the adsorption and condensation of Cu on Mo(110). Fitting the ADE results with various statistical-mechanical models gives good agreement with the desorption energies derived from the TDS, AT, and DT measurements. At coverages above two monolayers (ML) three-dimensional nucleation is seen in the kinetic measurements.     

Investigation of oxygen adsorption on Cu(110) by low-energy ion bombardment

The interaction of molecular oxygen with a Cu(110) surface is investigated by means of low energy ion scattering (LEIS) and secondary ion emission. The position of chemisorbed oxygen relative to the matrix atoms of the Cu(110) surface could be determined using a shadow cone model, from measurements of Ne⁺ ions scattered by adsorbed oxygen atoms. The adsorbed oxygen atoms are situated 0.6 ± 0.1 Å below the midpoint between two adjacent atoms in a 〈100〉 surface row. The results of the measurements of the ion impact desorption of adsorbed oxygen suggest a dominating contribution of sputtering processes. Ion focussing effects also contributes to the oxygen desorption. The ion induced and the spontaneous oxygen adsorption processes are studied using different experimental methods. Sticking probability values obtained during ion bombardment show a strong increase due to the ion bombardment.     

The adsorption of water on clean and oxygen covered Cu(110)

The water adsorption on clean and oxygen precovered Cu(110) surfaces is studied by means of UPS, LEED, work function measurements and ELS. At 90 K on the clean surface molecular water adsorption is indicated by UPS. The H₂O molecules are bonded at the oxygen end and the H-O-H angle is increased as compared with the free molecule. In the temperature range between 90 and 300 K distorted H₂O molecules and adsorbed hydroxyl species (OH) are detected, which are desorbed at room temperature. On an oxygen covered surface hydroxyl groups are formed by dissociation of adsorbed water molecules at a lower temperature than on the clean surface. Multilayers of condensed water are found below 140 K in both cases.     

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.     

In-situ observation of oxygen adlayer formation on Cu(110) electrode surfaces

In-situ atomic force microscopy (AFM) was used to image Cu(110) single crystals in aqueous solutions during the initial stages of oxidation. Images obtained in pH 2.5–2.7 HClO₄ and H₂SO₄ solutions revealed the growth of oxygen adlayers consisting primarily of [001] oriented chains. A majority of these chains (ca. 70%) were arranged in (2 × 1) and (3 × 1) structures. These chain structures were observed in the thermodynamically forbidden region of the pH-potential phase diagram, which indicates that stable oxygen adlayers develop prior to bulk oxide formation.     

Coadsorption of oxygen and water at Ni(110) surfaces

The interaction of water with oxygen covered Ni(110) surfaces has been studied using high resolution electron energy loss spectroscopy (HREELS). As suggested by a recent TDS/ESDIAD study, it is found that hydroxyl groups are formed at the surface which are stable even above the water-desorption temperature.