Overpotential deposition of Ag monolayer and bilayer on Au(1 1 1) mediated by Pb adlayer underpotential deposition/stripping cycles

Ultra-thin Ag films on the Au(1 1 1) surface were prepared via overpotential deposition (OPD) in the presence of Pb²⁺ ions. By carrying out repetitive Pb adlayer underpotential deposition (UPD) and stripping cycles during Ag bulk deposition, the two-dimensional growth of Ag films was significantly enhanced in high OPD. The Ag monolayer sample was made by comparing the voltammetry curves, in which the signatures for Pb adlayer UPD on Au(1 1 1) changed to that on Ag(1 1 1). As demonstrated by the X-ray specular reflectivity measurements, nearly complete monolayer and bilayer films can be made with optimized deposition procedures. On subatomic scale, however, we found that these films have significant higher root-mean-square displacement amplitudes than those underpotentially deposited Ag monolayer and bilayer on either Au(1 1 1) or Pt(1 1 1).     

Quantum-size effects in photoemission from ultra-thin films:: Theory and application to Cu-films on fcc-Co(001)

We report on detailed calculations of quantum-size effects on the electronic structure of the valence-band regime and their manifestation in photoemission. Model calculations reveal the basic features of photoemission from quantum-well states (QWS). First, emission from QWS shows intensity variations with photon energy which is similar to that of semi-infinite systems, despite the discrete binding energies of the QWS. Second, conservation of the wave-vector component normal to the surface is directly related to the film thickness. Numerical calculations within the relativistic one-step model of photoemission show that these effects should be observable in ‘real’ systems. This is demonstrated to be the case for Cu films on fcc-Co(001).     

Photoemission study of Ag nanofilm grown on pseudomorphic fcc Fe(1 0 0)

An angle-resolved photoemission study for Ag nanofilm grown on pseudomorphic metastable-fcc-phase Fe(1 0 0) has been done in order to investigate in detail the quantized electronic structures. From the low-energy electron-diffraction and angle-resolved photoemission spectra, it is found that the present Ag nanofilms were grown in the direction of [1 1 1] on pseudomorphic fcc Fe(1 0 0) substrates. The angle-resolved photoemission spectra of Ag nanofilms grown on pseudomorphic fcc Fe(1 0 0) exhibit the features derived from Shockley-type surface state and additional fine-structures derived from the quantized state of Ag sp valence electron. The experimental nanofilm-thickness dependence of binding energies of these quantized states is compared with the theoretical calculation based on the phase accumulation model, taking into account the phase shifts of electron reflection at both interfaces of the Ag nanofilm. From these results, we discuss the quantized electronic structure in Ag nanofilm grown on pseudomorphic fcc Fe(1 0 0).     

Adsorption of Ag on Si(1 0 0) surface

The chemisorption of one monolayer Ag atoms on an ideal Si(1 0 0) surface is studied by using the self-consistent tight-binding linear muffin-tin orbital method. The adsorption energies (E_ad) of different sites are calculated. It is found that the adsorbed Ag atoms are more favorable on C site (fourfold site) than on any other sites on Si(1 0 0) surface, the polar covalent bond is formed between Ag atom and surface Si atom, a Ag and Si mixed layer does not exist and does form an abrupt interface at the Ag–Si(1 0 0) interface. This is in agreement with the experiment results. The layer-projected density of states is calculated and compared with that of the clean surface. The charge transfer is also investigated. Comparing with the Au/Si(1 0 0) system, the interaction is weaker between Ag and Si than between Au and Si.     

Electronic properties of (Co, Ag) self-organized nano dots on Au(1 1 1) vicinal surfaces

Electronic properties of (Ag, Co) nanostructures grown on Au(1 1 1) vicinal surfaces have been studied by angle resolved photoemission spectroscopy (ARPES), scanning tunneling microscopy and spectroscopy (STM/STS). The growth and self-assembling of Co and Ag nano dots on Au(7 8 8) surface are described. Co island growth leads to the formation of repulsive energy barriers for the surface state, and subsequently to the appearance of confined states in between each group of four Co dots. On the contrary, when Ag nano dots are grown, the potential barrier for the surface electrons is not enough to suppress their dispersive behavior. Nevertheless, inside Ag islands appear new quantized states whose energies can be tailored by varying the deposition rate of the adsorbate and/or the Miller index of the vicinal surfaces. In both systems, high homogeneity of the electronic properties is achieved over a macroscopic scale.     

Growth and electronic properties of ultra-thin Ag films on Ni(1 1 1)

We studied the growth mode and electronic properties of ultra-thin silver films deposited on Ni(1 1 1) surface by means of scanning tunnelling microscopy (STM) and angle resolved photoemission spectroscopy (ARPES). The formation of the 4d-quantum well states (QWS) was analysed within the phase accumulation model (PAM). The electronic structure of the 1 ML film is consistent with the silver layer which very weakly interacts with the supporting surface. The line-shape analysis of Ag-4d_xz,yz QWS spectrum support the notion of strong localization of these states within the silver layer. The asymmetry of the photoemission peaks implies that the decay of the photo-hole appears to be influenced by the dynamics of the electrons in the supporting surface.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

Local spectroscopy of two-dimensional states in Na films on Cu(111)

Alkali overlayers on noble metal surfaces exhibit two-dimensional electronic states. We investigated the electronic structure of Na on Cu(111) at T=5 K with scanning tunneling spectroscopy. In agreement with photoelectron spectroscopy we found two electronic bands close to the Fermi energy which correspond to quantum well states (QWS). In second monolayer islands, confinement of the QWS was observed.     

Potential-induced strain relaxation in au mono- and bilayer films on Pt(111) electrode surfaces

In situ scanning tunneling microscopy observations of 1-2 monolayer thick Au films on Pt(111) electrodes are presented, which show a complex, potential-dependent structural phase behavior of the Au film. Starting from a pseudomorphic structure at <0.35 V(Ag/AgCl), a sequence of transitions into dislocation network structures occurs with increasing potential: (1x1)--> "striped phase" --> "hex phase" in the Au bilayer, (1x1)--> striped phase in the Au monolayer. This is explained by a reduction of the in-plane stress in the Au surface layer(s) due to anion adsorption and a strain energy minimization as described by the Frenkel-Kontorova model.     

Morphological modifications of Ag/Cu(111) probed by photoemission spectroscopy of quantum well states and the Shockley surface state

Epitaxial ultra-thin Ag films grown on Cu(111) have been investigated by angle-resolved photoemission spectroscopy. The thickness dependence of the binding energy for the Shockley surface state at 300 K could be determined accurately in films up to 5 ML thick. Furthermore, we observe drastic changes in the film morphology after annealing to 450 K. Spectral modifications in the shape of the quantum-well states (QWS), characteristic for these ultra-thin silver films, prove that the surface morphology is homogeneous. The photoemission spectra also indicate that the silver film bifurcates to form a film exhibiting two distinct film thicknesses. For all levels of silver coverage, we identify surface regions that are 2 ML thick, while the thickness of the remaining surface depends on the amount of deposited silver. The almost purely Lorentzian line-shape of the spectral features corresponding to the two different surface regions show that both surface areas are atomically flat. PACS 68.55.Jk; 73.20.At; 73.21.Fg; 79.60.Dp     

Quasi-particle spectrum and density of electronic states in AA- and AB-stacked bilayer graphene

The present work deals with the analysis of the quasi-particle spectrum and the density of states of monolayer and bilayer (AB- and AA-stacked) graphene. The tight binding Hamiltonian containing nearest-neighbor and next-nearest neighbor hopping and onsite Coulomb interaction within two triangular sub-lattice approach for monolayer graphene, along-with the interlayer coupling parameter for bilayer graphene has been employed. The expressions of quasi-particle energies and the density of states (DOS) are obtained within mean-field Green’s function equations of motion approach. It is found that next-nearest-neighbour intralayer hopping introduce asymmetry in the electronic states above and below the zero point energy in monolayer and bilayer (AA- and AB-stacked) graphene. The behavior of electronic states in monolayer and bilayer graphene is different and highly influenced by interlayer coupling and Coulomb interaction. It has been pointed out that the interlayer coupling splits the quasi-particle peak in density of states while the Coulomb interaction suppresses the bilayer splitting and generates a gap at Fermi level in both AA- and AB-stacked bilayer graphene. The theoretically obtained quasi-particle energies and density of states in monolayer and bilayer (AA- and AB-stacked) graphene has been viewed in terms of recent ARPES and STM data on these systems.     

Electrical conductance at initial stage in epitaxial growth of Pb, Ag, Au and In on modified Si(1 1 1) surface

The electronic properties of thin metallic films of Pb, Ag, Au and In atoms deposited at 105 K on well defined metallic surface, i.e. Si(1 1 1)-(6 × 6)Au surface with 10 ML of annealed Pb, were investigated using four-point probe method in UHV condition. The structure of the substrate and deposited metals were monitored by the RHEED system. The electrical conductance, measured during the deposition of In and Pb atoms, shows the local minimum for the coverage equals about 0.3 ML whereas for Au and Ag atoms the conductance decreases during the first monolayer growth. For Au atoms the local maximum in the conductance was observed for the coverage about 0.55 ML, which can be connected with localized states. To describe theoretically the conductance behavior the tight-binding Hamiltonian and equation of motion for the Green’s function were used and good qualitative agreement was obtained.     

Band structure of Au layers on the Ru(0001) and graphene/Ru(0001) surfaces

The electronic structures of Au monolayers on the Ru(0001) and graphene-coated Ru(0001) surfaces have been calculated by DFT method using the supercell (repeated-slab) approach. The local densities of states (LDOS) and band structures of the monolayer and bilayer Au films adsorbed on the graphene/Ru(0001) and those of free hexagonal Au layers are found to be very similar. This result indicates that the monolayer graphene almost completely screens the Au layers from the Ru(0001) substrate surface, so that electronic properties of Au films adsorbed on graphene are determined predominantly by the electronic structure of the Au adlayers, essentially independent on the electronic structure of the substrate surface.     

Thermal stability of atomically flat metal nanofilms on metallic substrates

By means of variable temperature scanning tunneling microscope we studied the morphology and electronic structure of Pb films grown on Cu(1 1 1). Due to the spatial confinement of electrons, the islands display quantized energy levels. At 300 K, Pb forms 3D nanostructures with magic heights, that correspond to islands having a quantum well state (QWS) far from the Fermi energy. Below 100 K Pb grows in a quasi-layer-by-layer fashion. The QWS that develop in the films determine their total energy and, accordingly, their thermal stability. Films of particularly magic thickness are stable upon heating to 300 K.     

Density functional investigation of structural and electronic properties of small bimetallic silver–gold clusters

Structural and electronic properties of bimetallic silver–gold clusters up to eight atoms are investigated by the density functional theory using Wu and Cohen generalized gradient approximation functional. By substitution of Ag and Au atoms, in the optimized lowest energy structures of pure gold and silver clusters, we determine the ground state conformations of the bimetallic silver–gold ones. We reveal that Ag atoms prefer internal positions whereas Au atoms prefer exposed ones favoring charge transfer from Ag to Au atoms. For each size and composition, binding energy, HOMO–LUMO gap, magnetic moment, vertical ionization potential, electron affinity and chemical hardness were calculated. On increasing the size of the cluster by varying number of Ag atoms with fixed number of Au ones, vertical ionization potential and electron affinity show obvious odd–even oscillations consistent with the pure Ag and Au clusters. Au atoms inclusion in the cluster increases the binding energy and vertical ionization potential, indicating higher stability as the number of Au atoms grows. The variation of chemical hardness with the composition in a cluster with the same size shows peaks when the number of Ag atoms is greater than or equal to Au ones, corresponding to transition from planar to tri-dimensional structures. For clusters with even number of atoms, the peaks indicate that the clusters with the same number of Ag and Au atoms are the most stable ones. Analyzing the density of states, we found that increasing the concentration of Ag atoms affects the energy separation between the HOMO and the low lying occupied states.     

Kinetics of facile bilayer island formation at low temperature: Ag/NiAl(110)

Facile nucleation and growth of bilayer Ag(110) islands on NiAl(110) is observed by STM for Ag deposition at temperatures as low as 127 K. Density functional theory analysis for supported Ag films determines adatom adsorption energies (which favor bilayer islands), interaction energies, and diffusion barriers. Analysis of an atomistic lattice-gas model incorporating these energies elucidates the role of strongly anisotropic interactions in enabling the upward mass transport needed for bilayer island formation.     

Realization of an atomic sieve: Silica on Mo(1 1 2)

The adsorption of Pd, Ag and Au atoms on a porous silica film on Mo(1 1 2) is investigated by scanning tunneling microscopy and density functional theory. While Pd atoms are able to penetrate the holes in the silica top-layer with virtually no barrier, Ag atoms experience an intermediate barrier value and Au atoms are completely unable to pass the oxide surface. The penetration probability does not correlate with the effective size of the atoms, but depends on their electronic structure. Whereas Pd with an unoccupied valence s-orbital has a low penetration barrier, Ag and Au atoms with occupied s-states experience a substantial repulsion with the filled oxide states, leading to a higher barrier for penetration. In the case of Ag, the barrier height can be temporally lowered by promoting the Ag 5s-electron into the support. The Mo-supported silica film can thus be considered as a primitive form of an atomic sieve whose selectivity is controlled by the electronic structure of the adatoms.     

CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

Effect of interfacial alloying on the surface plasmon resonance of nanocrystalline Au-Ag multilayer thin films

Nanocrystalline Au and Ag in multilayer thin film form with Au/Ag/Au structure were prepared by high pressure (∼40 Pa) d.c. sputtering techniques. The Ag concentrations in Ag_xAu_1-x films were changed from x = 0 to 1. These multilayer films with varying Ag concentration showed significant changes in microstructures obtained from TEM and XRD analyses. The optical absorption spectra of these multilayer films showed a single plasmon band confirming the formation of Au-Ag alloy. We ascribe this alloying to the interfacial reactions in nanophase limited at the Au-Ag interface. The red-shift and broadening of the plasmon bands with the increase in silver concentration could be associated to the increase in size of the nanoparticles and its distribution. The observed red shift in the plasmon band may be associated with the change in electronic structure at the Au-Ag interface due to configuration mixing of the atomic energy levels of Au and Ag. Received 17 October 2002 / Received in final form 26 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in