局域功函数图像及其在Cu(111)-Au/Pd表面的应用

用扫描隧道显微镜（STM）对Cu(111)-Au和Cu(111)-Pd表面的局域功函数进行了研究.通过 测量隧道电流对针尖样品间距的响应，得到了与STM形貌图一一对应的表面局域功函数图像. 实验发现，Au/Pd覆盖层和Cu衬底间的功函数有明显的不同.Pd薄膜的功函数甚至超过了其体 本征值，且功函数在台阶处变小.用偶极子的形成解释了台阶处功函数的降低.这一工作表明 ，用测量局域功函数的方法容易区分表面上不同的元素，并具有纳米尺度的空间分辨率. 关键词： 扫描隧道显微镜 局域功函数 台阶     

Bromine adsorption on Cu(111)

The dissociative chemisorption of molecular bromine on Cu(111) at 300 K has been studied using ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function change measurements. A (√3 × √3)R30° structure is formed initially at a bromine coverage of 0.33 ML. This then converts to a (9√3 × 9√3)R30° compression structure with a coverage of 0.41 ML. The coincidence distance of the compression structure is determined entirely by the van der Waals diameter of adsorbed bromine. The applicability of using the van der Waals diameters of the three halogens, Cl, Br and I, to predict the saturation compression structures on Cu(111), is discussed.     

The Tamm surface state on Cu(111) and Ag(111)

It is shown, that the well-known d-electron Tamm surface-state emission observed in photoelectron spectra from Cu(111) at the M̄ point in the surface Brillouin zone, is indeed due to such a surface state and not a bulk band transition as recently suggested L. Wallden, Solid State Commun. 59, 205 (1986). A similar surface state on Ag(111) is reported.     

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.     

The anomalous RHEED patterns observed from (111)Ag-(111)Cu bilayers

RHEED patterns obtained from thin expitaxial bilayers consisting of Ag grown on smooth (111)Cu surfaces have been shown by Gradmann and Krause to contain anomalous reflections. Previously, these reflections were interpreted as due to a regular arrangement of interfacial dislocations or to multiple diffraction effects. In the present work a thin film technique was used to form smooth, easily detachable (111)Ag/Cu bilayers from which RHEED patterns containing these extra reflections were obtained. These films were grown, annealed, and examined in situ by UHV-RHEED techniques. They were then removed from the vacuum system, detached from their substrates and examined by TEM and TED. Thus, contrary to previous work, the present observations consisted of a series of experiments using RHEED, TED, and TEM carried out on the same specimen. No evidence was obtained to indicate that the anomalous reflections were due to interfacial dislocations. Rather, all the observed phenomena could be explained entirely by multiple diffraction effects.     

Quantum confinement in monatomic Cu chains on Cu(111)

The existence of one-dimensional (1D) electronic states in Cu/Cu(111) chains assembled by atomic manipulation is revealed by low-temperature scanning tunneling spectroscopy and density functional theory (DFT) calculations. Our experimental analysis of the chain-localized electron dynamics shows that the dispersion is fully described within a 1D tight-binding approach. DFT calculations confirm the confinement of unoccupied states to the chain in the relevant energy range, along with a significant extension of these states into the vacuum region.     

Oscillating indirect coupling of perpendicular magnetized Co(111)-monolayers through Cu(111)

Oscillating indirect coupling has been observed between perpendicularly magnetized Co(111)-monolayers on Cu(111). through a Cu(111)-interlayer. Contrarily, a weak indication of oscillation only was observed between in-plane magnetized Co(111)-films containing 5 monolayers each. Possible mechanisms for the strongly differing coupling behaviour observed in the Cu/Co(111) system are discussed.     

Auger spectra of carbon monoxide chemisorbed on Pt(111) and Cu(111)

The Auger spectra of carbon monoxide adsorbed on Pt(111) and Cu(111) are compared. The characteristic features now regarded as a fingerprint of this adsorbed species are observed, even for the weakly adsorbed CO on copper which gives complex X-ray photoelectron spectra. No coverage dependence of the spectra was observed on either substrate. The C lsVV spectrum of CO/Cu(111) is dominated by transitions involving the “screening” electron in the 2π orbital.     

Formation and diffusion of S-decorated Cu clusters on Cu(111)

S-decorated Cu trimers are a likely agent of S-enhanced Cu transport between islands on Cu(111). According to ab initio calculations, excellent S bonding to trimer-Cu dangling valence results in an ad- Cu(3)S(3) formation energy of only approximately 0.28 eV, compared to 0.79 eV for a self-adsorbed Cu atom, and a diffusion barrier < or =0. 35 eV.     

Auger line shape changes in epitaxial (111)Pd/(111)Cu films

Epitaxial Pd films ranging in thickness from a few tenths of a monolayer up to many monolayers were formed on (111)Cu substrate films at room temperature under UHV conditions. The growth of these Pd films was monitored in situ by Auger electron spectroscopy. The line profiles of the Cu MMM (61 eV) and Pd MVV (329 eV) AES doublets varied significantly with the amount of Pd deposited. A new measure of the AES doublet line profile, called the R-factor, was defined. A graph R_pd versus Pd film thickness shows a sharp decline with increasing thickness. Superimposed on the major trend is a cyclical variation. A corresponding periodicity in R_cu was observed for the Cu MMM (61 eV) AES doublet. The results suggest that the R-factor provides a direct measure of changes in the electronic structures of the overgrowth and substrate films as the former thickens by a layer-growth mechanism.     

Electron resonances in VLEED from Cu(111)

The sensitivity of the VLEED I–V curves to the shape and the position of the barrier is shown for the image- type surface barriers. For demonstration and comparison with experimental data the intensities of specularly reflected electron beams from Cu(111) are computed by dynamical theory of electron diffraction. Image plane position changes and modifications of the saturation shape of the surface barrier induce pronounced changes in the I–V curves calculated with the image-type barrier. Presented at the X-th Symposium on Suface Physics, Prague, Czech Republic, July 11–15, 2005.     

Electronic structure of the Cu(111) surface

Self-consistent electronic structure calculations are reported on bulk Cu, and 3- and 5-layer Cu films. These yield a size insensitive work function, φ = 5.0±.1 eV, and a surface energy of 0.75 eV, in agreement with experiment. Good size convergence of the film potential permits the construction of a self-consistent potential for an 11-layer Cu(111) film, whose spectral properties we studied. A prominent p-like surface band was found within 0.1 eV of experiment, serving as a check on the surface potential.     

NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study

NO dissociation on Cu(111) and Cu(2)O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NO(x) reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu(2)O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu(2)O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu(2)O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.     

Interactions of CO molecules adsorbed on oxidised Cu(111) and Cu(110)

Reflection absorption infrared spectroscopy has been used in conjunction with LEED and surface potential measurements to study low temperature CO adsorption on the oxidised Cu surfaces Cu(111)O|$\text{3}\text{2}\text{?}\text{2}$|, Cu(110)O(2 × 1) and Cu(110)Oc(6 × 2). On all three surfaces adsorption at 80 K yields surface potential changes in excess of 0.6 V and does not lead to the formation of an ordered overlayer. At high coverages the adsorption enthalpy is lower than on the clean surfaces. Infrared spectra show the growth of a doublet band with components initially at 2100 and 2117 cm^?1 on the oxidised Cu(111) surface. Similar features seen on the oxidised Cu(110) surfaces are accompanied by a band at 2140 cm^?1: a very weak band at the same frequency on oxidised Cu(111) is attributed to defect sites. Studies of the temperature dependence of the spectrum from oxidised Cu(111) lead to the conclusion that two different binding sites are occupied. Spectra of ${}^{12}\text{CO}{}^{13}\text{CO}$ mixtures show that the molecules occupying these sites are in close proximity to each other, and that the spectrum is subject to large but opposing coverage-dependent frequency shifts.     

On the structure of CO adlayers on Cu(100) and Cu(111)

Alternative models for the high coverage compressed overlayers of CO on copper (100) and (111) are proposed in which the LEED patterns previously attributed to out-of-registry, uniformly compressed structures are re-interpreted in terms of adsorption on linear and bridged sites. The models provide a simpler explanation for the small influence of compression on the frequency of the infrared adsorption bond near 2000 cm^?1 compared with the large change of surface potential.     

Interaction of CO with Cu(111)-Fe

The interaction of CO with a Cu(111) crystal alloyed with different amounts of iron is studied with ellipsometry and AES. Both molecular and dissociative adsorption are observed. The final coverages of oxygen and carbon are equal and such that the sum is the same or larger than the mole fraction of iron in the surface layer. The amount of molecularly adsorbed CO does not increase when a quantity of more than about four monolayers of iron is deposited. This is most probably due to the fact that the iron enrichment of the outer surface layer ceases as well. The isosteric heat of adsorption of CO on the Cu(111)-Fe crystal is 70±15 kJ/mol, independent of coverage and iron content of the surface within experimental error.