Cluster–surface interaction studied by time-resolved two-photon photoemission

n ⁺ clusters (n=2-9)deposited onto highly oriented pyrolytic graphite (HOPG) substrates at liquid nitrogen temperatures. The deposition was carried out with variable kinetic energies of the clusters. Clusters deposited with high kinetic energy (up to 60 eV/cluster) become fragmented upon impact. For low deposition energies (1–4 eV/cluster) the size dependence of the photoelectron spectra reveals a pronounced odd/even effect, which is well known for gas phase silver clusters. This indicates that the soft deposited clusters retain their size and identity on the sample. The phase of the odd/even effect suggests that transient negatively charged cluster ions serve as an intermediate step in the two-photon photoemission process. The lifetime of the anions rises with cluster size. This is attributed to an increasing electronic density of states for larger clusters. Received: 26 October 1998 / Revised version: 16 December 1998     

Processes involved in the formation of silver clusters on silicon surface

We analyze scanning electron microscopy measurements for structures formed in the deposition of solid silver clusters onto a silicon(100) substrate and consider theoretical models of cluster evolution onto a surface as a result of diffusion and formation of aggregates of merged clusters. Scanning electron microscopy (SEM) data are presented in addition to energy dispersive X-ray spectrometry (EDX) measurements of the these films. Solid silver clusters are produced by a DC magnetron sputtering source with a quadrupole filter for selection of cluster sizes (4.1 and 5.6 nm or 1900 and 5000 atoms per cluster in this experiment); the energy of cluster deposition is 0.7 eV/atom. Rapid thermal annealing of the grown films allows analysis of their behavior at high temperatures. The results exhibit formation of cluster aggregates via the diffusion of deposited solid clusters along the surface; an aggregate consists of up to hundreds of individual clusters. This process is essentially described by the diffusion-limited aggregation (DLA) model, and thus a grown porous film consists of cluster aggregates joined by bridges. Subsequent annealing of this film leads to its melting at temperatures lower than to the melting point of bulk silver. Analysis of evaporation of this film at higher temperatures gives a binding energy in bulk silver of ɛ₀= (2.74 ± 0.03) eV/atom. The text was submitted by the authors in English.     

Fragmentation of plasma resonances in open-shell silver cluster ions

Summary We study the fragmentation of the dipole collective states in silver cluster ions by looking at the coupling with surface oscillations and deformations of a dropletlike structure. This coupling is found to be crucial in order to reproduce the experimental photoabsorption data in open-shell clusters.     

Tunnelling spectroscopy on silver islands and large deposited silver clusters on Ge(001)

Morphology and electronic properties of silver islands and deposited silver clusters on Ge(001) have been studied using scanning tunnelling microscopy (STM) and spectroscopy (STS) at low temperatures. Already the clean surface bears an interesting electronic structure, which is obvious from the STS. The tunnelling spectra exhibit strong peaks associated with dangling bond-derived surface states and an antibonding σ-state of the surface dimer. For silver islands of only few monolayers in height, complex spectra are interpreted to be dominated by metal–semiconductor interface states. These islands show energy gaps which are not observed for larger ones beyond 1 nm in height. Spectra of the larger islands contain a series of distinct peaks originating from lateral and three-dimensional electron confinement, respectively. Silver clusters – preformed in the gas phase using a cluster source – have been fabricated, size selected and deposited onto germanium(001). In tunnelling spectra dips at the Fermi level are accompanied by two maxima. These characteristics seem to be almost independent from the cluster size. Additional weak structures are found at higher bias voltages, which are understood in terms of quantized states. PACS 36.40.Cg; 61.46.+w; 73.20.At     

Deformation of slow liquid and solid clusters upon deposition: A molecular-dynamics study of Al cluster impact on an Al surface

Using molecular-dynamics simulation, we investigate the self-deposition of Al_n clusters (n < 4000) on an Al substrate at velocities below the velocity of sound. Both cold crystalline and hot liquid clusters are studied. We examine the cluster deformation after impact on the surface, which we quantify by its height and base radius. At a given cluster velocity, the shape of deposited crystalline clusters is rather independent of the cluster size; only at small cluster sizes, n ? 40, the clusters are less strongly deformed. With increasing cluster size, liquid clusters are more strongly deformed than crystalline clusters. Faster projectiles become more strongly flattened by the deposition process. Even clusters depositing with vanishing velocity show a finite deformation, which is considerable for smaller clusters. At large cluster speed, clusters penetrate deeper into the (1 0 0) surface than into the (1 1 1) surface and also deform more strongly.     

Instability driven fragmentation of nanoscale fractal islands

Formation and evolution of fragmentation instabilities in fractal islands, obtained by deposition of silver clusters on graphite, are studied. The fragmentation dynamics and subsequent relaxation to the equilibrium shapes are controlled by the deposition conditions and cluster composition. Sharing common features with other materials' breakup phenomena, the fragmentation instability is governed by the length-to-width ratio of the fractal arms.     

银原子在液体基底上的凝聚特性

研究了沉积在液体基底表面上的银原子的扩散和凝聚特性．实验结果表明：银原子在液体表面先形成准圆形的团族，然后通过无规扩散而逐渐凝聚成具有分枝状的凝聚体．准圆形团簇的平均半径以及凝聚速率均随沉积速率的变化而变化．还提出了一个凝聚速率概率模型，计算结果与凝聚速率的实验曲线相符合． 关键词：     

Molecular dynamics simulation of Cu_n clusters scattering from a single-crystal Cu(111) surface: The influence of surface structure

By performing a molecular dynamics simulation, fragmentation of Cu_n clusters scattering from a single-crystal Cu(111) surface is studied. The interactions among copper atoms are modeled by tight-binding potential, and the positions of the copper clusters at each time step are calculated by integrating the Newton equations of motion. The percentage of unfragmented clusters depends on the incident velocities, angles of incidence, and surface structure. The influence of surface structure on the fragment distribution is discussed, and the clusters appear to be more stable under an axial channeling condition. The fragment distribution shifting toward the small fragment range for cluster scattering along a random direction is confirmed, indicating that the cluster undergoes more intensive fragmentation.     

Deposition mechanism of nano-structured single-layered C36 film on a diamond （100） crystal plane

The Brenner-LJ potential is adopted to describe the interaction between C36 clusters and diamond surface, and the deposition mechanism of multi-C36 clusters on the diamond surface is also studied by using the method of molecular dynamics simulation. The simulation results show that the competition effects of two interactions, i.e. the interaction between cluster and cluster and the interaction between cluster and crystal plane, are studied, and then the influence of these competition effects on C36 cluster deposition is analysed. The finding is that when an incident energy is appropriately chosen, C36 clusters can be chemically adsorbed and deposited steadily on the diamond surface in the form of single-layer, and in the deposition process the multi-C36 clusters present a phenomenon of energy transmission. The experimental result shows that at a temperature of 300K, in order to deposit C36 clusters into a steady nanostructured single-layered film, the optimal incident energy is between 10 and 18 eV, if the incident energy is larger than 18 eV, the C36 clusters will be deposited into an island nano-structured film.     

The role of direct surface interaction in surface enhanced Raman scattering by pyridine and CO on silver

The surface enhanced Raman scattering (SERS) phenomenon due to pyridine on silver and CO on silver in ultra-high vacuum (UHV) has been compared. The study was carried out for two different kinds of silver surfaces, island films and “cold” films on island films. We have reported earlier that it was necessary to warm the samples to about 70K in order to observe the full surface enhanced Raman spectrum when the pyridine was deposited on silver island films on sapphire substrates at liquid He temperatures. We call this the effect of a “low temperature anneal” and the present work indicates that this effect is more general than we originally thought. It has also been found that island films exhibit enhanced Raman scattering for pyridine but not for CO, although “cold” films enhance the Raman scattering of both CO and pyridine. This is the first clear indication that molecular specificity may be a part of the SERS phenomenon. The interpretation of these observations depends critically on our understanding of the SERS phenomenon.     

VUV-photoelectron spectroscopy on lead clusters deposited from the pulsed arc cluster ion source (PACIS)

Lead clusters grown in a pulsed arc cluster ion source (PACIS) are soft-landed under UHV conditions on cooled polycrystalline silver targets. VUV-photoelectron spectroscopy with light from the synchrotron BESSY applied to mass-selected clusters on cold (160 K) substrates shows that the Pb 5d core level binding energies depend on cluster size and-only beyond a critical amount of deposited clusters-on the coverage . A decreasing particle size induces a core level shift towards lower binding energy with respect to the bulk value, the maximum shift being –0.33 eV. The same value is achieved by atom deposition and can be explained by a Born-Haber cycle. The limits for small two-dimensional and large three-dimensional clusters will qualitatively be discussed by the same model. Deposition on a warm substrate, however, leads-at least for small systems-to a gradual line shift with .     

Experimental and Theoretical Studies on the Interaction between Isonicotinic Acid Molecules and Silver Nanoclusters

The present paper describes the studies on the adsorption behavior and charge transfer from isonicotinic acid to silver nanoparticles with experiment and theory. Compared with UV–Visible adsorption spectrum, the adsorption spectrum of Ih-Ag₁₃ cluster was quite good agreed with that of silver colloidal nanoparticle. So that one Ag₁₃ cluster as a substrate was used to simulate Raman frequencies of the adsorption configuration. Here, it is demonstrated the calculated Raman spectra are in good agreement with experimental results. The analysis of Mulliken charge was obtained by density functional theory, which indicated the charge characteristics of Ag₁₃ nanoparticle. Once isonicotinic acid molecules were adsorbed on sliver clusters, the charges transfer from isonicotinic acid to silver clusters, so that the surface charges of silver clusters are uneven.     

A novel approach towards the production of luminescent silicon nanoparticles: sputtering, gas aggregation and co-deposition with H2O

Silicon clusters were produced by sputtering of a p-doped Si target and aggregation of the Si atoms in an argon gas atmosphere. The clusters were deposited in ultra high vacuum onto either (i) carbon transmission electron microscope (TEM) grids or (ii) a liquid nitrogen cooled finger on which a thick layer of ice was co-deposited during the exposure to the cluster beam. The ice layer containing the clusters was melted to form a liquid sample which showed luminescence peaking at 421 nm when excited at 307.5 nm. The luminescence is attributed to electron-hole recombination in oxygen deficient defects in the Si–SiO₂ interface region. TEM images of the nanoparticles deposited on the carbon grids show spherical particles with diameters ranging from 4 to 50 nm, flake-like structures or nanotube-like shapes. Grids with higher deposited densities reveal clusters that are agglomerated into chains, TEM images of the dried liquid sample show a network of fibres indicating that growth into fibres is further promoted when the clusters gain mobility in the melted ice.     

团簇淀积纳米结构薄膜的计算机模拟

对团簇的淀积方式作了简介。着重对团簇的淀积过程进行了计算机模拟,从中得出了淀积的尺寸分布与团簇在衬底上的徙动长度有关,而团簇的聚合长大存在一临界尺寸。并给出低能Ｐｂ团簇在碳膜表面的徙动长度和聚合的临界尺寸。     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

Thermal and chemical nanofractal relaxation

We studied shape relaxation of nano-fractal islands, during annealing, after their growth from antimony cluster deposition on graphite surface. Annealing at 180^°C shows evidence of an increase of the fractal branch width with time followed by branch fragmentation, without changing the fractal dimension. The time evolution of the width of the arm suggests the surface self-diffusion mechanism as the main relaxation process. With Monte Carlo simulations, we confirmed the observed behavior. Comparison is done with our previous results on fragmentation of nano-fractal silver islands when impurity added to the incident cluster promotes rapid fragmentation by surface self-diffusion enhancement [1].