Mobility and aggregation of free clusters soft landed on amorphous and crystalline carbon substrates

Neutral antimony clusters produced by a gas aggregation source have been deposited at room temperature on thin films of amorphous carbon and cleavage surfaces (0001) of graphite. Antimony islands generated from different mean size distributions of preformed clusters Sb_n(n = 4, 90, 150, 250, 600, 2000) have been investigated by transmission electron microscopy. Only compact islands have been observed on amorphous carbon, whereas an evolution from compact to dendritic shapes occurs on graphite substrate as the mean size of the deposited clusters increases. For clusters containing more than 150 atoms the dendritic islands exhibit a fractal character whose dimensional analysis yields a fractal dimension of 1.63 ± 0.07. The different models for island growth are discussed in the light of these results.     

Comparison of electronic structure development in gold clusters formed on amorphous and annealed carbon substrates

The growth of gold clusters vacuum deposited onto differently prepared carbon surfaces was studied by UV photoclectron spectroscopy. Variable photon energies were used to follow the evolution of band structure with cluster size. The development of electronic structure is markedly different for clusters formed on amorphous and annealed carbon substrates.     

Size and structure dependence of carbon monoxide chemisorption on cobalt clusters

We have carried out a series of ab initio calculations to investigate changes in the structural and magnetic properties of pristine cobalt clusters upon CO chemisorption. Our results show that binding energies of CO to 13-55 atom (0.5-1.5 nm) cobalt nanoparticles and preferred chemisorption sites depend on the cluster structure (whether fcc or icosahedral), size, and surface coverage. In addition, we find a strong influence of CO on the magnetism of the cluster, leading to magnetic moments smaller than in the bulk, at variance with pristine clusters which have magnetic moments larger than the bulk. Our findings suggest important changes in catalytic properties of cobalt at the nanoscale. Our theory suggests that at the nanoscale cluster size and surface coverage might control catalysis.     

Aldehyde-terminated amorphous carbon substrates for the fabrication of biomolecule arrays

Amorphous carbon thin films are easily deposited at room temperature, readily functionalized with alkene-containing molecules through a UV photochemical reaction, and provide a robust surface capable of supporting chemical and biomolecule array fabrication. Aldehyde-terminated amorphous carbon substrates were fabricated via the attachment of a 2-(10-undecen-1-yl)-1,3-dioxolane molecule. The surfaces were then deprotected in 1.5 M HCl to yield an aldehyde-terminated surface that is readily reactive with amine containing molecules. An array of amine-modified oligonucleotides was prepared on aldehyde-terminated surfaces prepared on both amorphous carbon and on gold self-assembled monolayers, and the fluorescence background, feature signal-to-noise ratio, and hybridization densities were compared. The aldehyde-terminated amorphous carbon substrates offer inherently lower background fluorescence intensity and a greater number of hybridization-accessible sites.     

Elemental distribution in fluorinated amorphous carbon thin films

Focused ion beam-secondary ion mass spectrometry (FIB-SIMS) with 20 nm spatial resolution has been used to analyze amorphous fluorinated carbon thin films, deposited by plasma assisted chemical vapor deposition (PACVD), at micro- to nano-scale. Mass spectra and ion imaging of film surface were acquired and the presence and distribution of contaminants were investigated. Surface images show the secondary ion distribution for F(-), CH(-), CF(-). A change in size and topology of fluorine-rich areas is correlated with film hardness and with microstructure transition from diamond-like to polymer-like, as indicated by infrared and Raman spectroscopies. Based on the surface distributions of CF(-) and CH(-) and on the vibrational spectroscopy results, a mechanism of fluorine substitution for hydrogen and an attempt to explain the film structure and microstructure is proposed.     

Size of free neutral CO2 clusters from carbon 1s ionization energies

Free neutral CO(2) clusters were produced by adiabatic expansion and characterized by carbon 1s (C1s) photoelectron spectroscopy using synchrotron radiation. The shift in C1s ionization energy (IE) between the cluster and the monomer, i.e., ΔIE = IE(cluster) - IE(monomer), was found to vary systematically with the experimental conditions. A functional relationship is established between the mean cluster size in the beam, , and ΔIE, in good agreement with theoretical calculations of shifts in ionization energy for model clusters. This makes it possible to use core-level photoelectron spectroscopy to monitor the mean cluster size and also to estimate from expansion conditions.     

Deposition of amorphous calcium carbonate hemispheres on substrates

The amorphous calcium carbonate (ACC) hemispheres were deposited on the mica and poly(diallyldimethylammonium chloride) modified surface. The form of the ACC deposit on the substrates can be controlled by modifying the substrate surface, the introduction of additives, or both. It demonstrated that substrates (insoluble matrix) and additives (soluble macromolecules) have significant influence on the crystallization of CaCO(3).     

EELS investigation of small gold clusters on mica substrates

Gold clusters with diameters from 2 to 10 nm are prepared by evaporation on mica substrates. They are investigated with low energy electron loss spectroscopy in the reflected beam and characterised in a transmission electron microscope. The energy loss spectra show a broadening of the plasma peak with decreasing particle size. The plasma frequency shifts to higher energies. The size dependence of the half width and of the plasma frequency is compared to known models. The results support the quantum box model of Genzel et al.     

Catalytic activity of electrolytic palladium deposits on porous nickel substrates

Catalytic activity of palladium layers in reduction of atmospheric oxygen and oxidation of methanol and ethanol in an alkaline medium was studied for electrolytic palladium deposits on porous nickel substrates by cyclic voltammetry on a rotating disk electrode.     

Experimental and theoretical investigation on binary semiconductor clusters of Bi/Si, Bi/Ge, and Bi/Sn

Bi(m)M(n)- (M = Si, Ge, Sn) binary cluster anions are generated by using laser ablation on mixtures of Bi and M (M = Si, Ge, Sn) samples and studied by reflectron time-of-flight mass spectrometer (RTOF-MS) in the gas phase. Some magic number clusters are present in the mass spectra which indicate that they are in stable structures. For small anions (m + n < or = 6), their structures are investigated with the DFT method and the energetically lowest lying structures are obtained. For the binary anionic clusters with the same composition containing Si, Ge, and Sn, they share similar geometric and electronic structure in the small size except that BiSi3-, BiSi5-, Bi2Si2-, Bi2Si3-, and Bi4Sn2- are different for the lowest energetic structures, and the ground states for all the anions are in their lowest spin states. The calculated VDE (vertical detachment energy) and binding energy confirm the obviously magic number cluster of BiM4- (M = Si, Ge, Sn), which agrees with the experimental results.     

Interactions of linear carbon clusters

Collisions of linear carbon clusters are investigated theoretically using the MINDO/3 method. It is shown that if a collision of two clusters transfers the system into a bound state, at the next step a four-or three-pronged star is formed. If the prongs are not closed in rings, the system evolves to a linear isomer due to “migration of atoms through the center”, which is a diffusion mechanism, by which the atoms overcome relatively small barriers to migrate through the center of the star from one prong to another. When a prong is reduced to two atoms, it is absorbed. If one or two pairs of prongs have time for cyclization, the final product is a monocyclic or bicyclic isomer. Institute of Theoretical and Applied Mechanics, Siberian Branch, Russian Academy of Sciences. Institute of Computational Technologies, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 6, pp. 983–990, November–December, 1995. Translated by I. Izvekova     

Reaction studies of carbon clusters

Reaction studies of carbon clustersC _n in the rangen=8–37, produced by laser vaporisation in a supersonic nozzle, have been investigated using time-of-flight mass spectrometry. Clear differences in reaction products formed on hydrogenation are detected which show that even and odd clusters behave quite differently and furthermore thatat least two different types of even cluster appear to exist. The reactivity patterns for clusters C _n withn=16, 18 and 22 are in a different class from those withn=20, 24, 26 ..., a behaviour consistent with the existence of closed cage fullerene structures for even clusters with 20 or more carbon atoms (other thann=22).     

Liquid chromatography of carbon clusters

Summary A comparison of three binary mobile phases in LC separation of C₆₀ and C₇₀ fullerences on chemically bonded 2,4-dinitroanilinopropyl (DNAP) stationary phase was carried out, n-Hexane-benzene has been found to be the best mobile phase for efficient separation of the all-carbon molecules permitting high loads in preparative LC.     

Binding energy per adatom in metal clusters adsorbed on metal substrates

In this paper the dependence of the binding energy per atom on the cluster size for metal clusters supported on metal substrates is studied. A semi-empirical Anderson-Newns-Grimley model is applied to calculate qualitatively the binding energy for neutral adatoms. The influence of the support on the even-odd oscillations is revealed and the competition between the adatom-adatom and the adatom-substrate interaction is discussed. The connection of the obtained results with some experimental measurements is shown.     

Comparison between the growth of gold particles onto MgO and amorphous carbon substrates by in situ electrical conductance measurements

The sheet conductance of gold condensates on MgO anda-C is expressed in terms of granulometric quantities. This expression enables us to follow the evolution of metal repartition on its substrate during the gold evaporation. The difference between the growth modes of these gold layers on MgO and ona-C is explained by the predominance of respectively nucleation and coalescence phenomena     

非晶碳纳米球的低温石墨化(英文)

The investigation by SEM/TEM, porosity, and X-ray diffraction measurements of the graphitization process starting from amorphous carbon nanospheres, prepared by glucose carbonization, is reported. Aspects studied are the annealing temperature in the 750–1000 °C range, the type of inert carrier gas, and time of treatment in the 2–6 h range. It is investigated how these parameters influence the structural and morphological characteristics of the carbon materials obtained as well as their nanostructure. It is shown that it is possible to maintain after graphitization the round-shaped macro morphology, a high surface area and porosity, and especially a large structural disorder in the graphitic layers stacking, with the presence of rather small ordered domains. These are characteristics interesting for various catalytic applications. The key in obtaining these characteristics is the thermal treatment in a flow of N2. It was demonstrated that the use of He rather than N2 does not allow obtaining the same results. The effect is attributed to the presence of traces of oxygen, enough to create the presence of oxygen functional groups on the surface temperatures higher than 750 °C, when graphitization occurs. These oxygen functional groups favor the graphitization process.     

Raman characterization of amorphous carbon films

Amorphous carbon films, deposited with the LASER-ARC technique, have been characterized using Raman scattering experiments at an excitation wavelength of 633 nm provided by a He-Ne laser. To distinguish between the homogeneous amorphous film and incorporated particles area resolved measurements have been carried out due to the laser spot diameter of 1 m. Typical diamondlike (DLC) films, grown near room temperature, show a broad Raman band between 1000 cm^–1 and 1800 cm^–1 fitted very well by two gaussian distributions. Films deposited at higher substrate temperatures reveal more graphitic features in the spectra. The spectra of particles consists of a graphite-like portion originated from the graphitic structure of the particle and a diamond-like portion caused by the covering DLC film. The degree of disorder and diamond-likeness in the film structure is quantified by the peak position, the full width at half maximum (FWHM) and intensity relation of the fitted D- and G-peaks.     

The structure of small carbon clusters

New non linear isomers of C _n forn=4, 5, 6 have been observed using the combination of the laser photodetachment technique and the Coulomb Explosion Imaging method. Electron affinities of these isomers were found to be lower than the corresponding known linear isomers. The structure of low electron affinity C₄ isomer was found to be rhombic in accordance with recent theory. Indications for the non linearity of the low electron affinity isomers of C₅ and C₆ are also presented.     

Photodissociation of noble metal-doped carbon clusters

Noble metal carbide cluster cations (MC(n)(+), M = Cu, Au) are produced by laser vaporization in a pulsed molecular beam and detected with time-of-flight mass spectrometry. Copper favors the formation of carbides with an odd number of carbon atoms, while gold shows marked drops in ion intensity after clusters with 3, 6, 9, and 12 carbons. These clusters are mass selected and photodissociated at 355 nm. Copper carbides with an odd number of carbons fragment by eliminating the metal from the cluster; for the small species it is eliminated as Cu(+) and for the larger species it is lost as neutral Cu. Copper carbides with an even number of carbons also lose the metal, but in addition to this they eliminate neutral C(3). This even-odd alternation, with the even clusters having mixed fragments, holds true for clusters as large as CuC(30)(+). No loss of C(2) is observed for even the largest clusters studied, indicating that fullerene formation does not occur. The gold carbide photodissociation data closely parallel that of copper, with even clusters losing primarily C(3) and odd ones losing gold. Comparisons to known carbon cluster ionization potentials give some insight into the structures of carbon photofragments. DFT calculations performed on CuC(3-11)(+) allow comparisons of the energetics of isomers likely present in our experiment, and metal-carbon dissociation energies help explain the even-odd alternation in the fragmentation channels. The simplest picture of these metal-doped carbides consistent with all the data is that the small species have linear chain structures with the metal attached at the end, whereas the larger species have cyclic structures with the metal attached externally to a single carbon.     

Size-dependent carbon monoxide adsorption on neutral gold clusters

We report on experiments probing the reactivity of neutral Au(n) clusters, n = 9-68, with carbon monoxide. The gold clusters are produced in a pulsed laser vaporization cluster source, operated at room temperature (RT) or at liquid-nitrogen temperature (LNT), pass through a low-pressure reaction cell containing CO gas, and are subsequently laser ionized. The reaction probabilities are determined by recording mass abundance spectra with time-of-flight mass spectrometry. The main observations are a strong temperature dependence and a remarkable size dependence. Upon cooling of the cluster source to LNT, the reactivity increases substantially. At LNT, the reaction probabilities for Au(n) with the first CO molecule are about a factor 10 higher than at RT. Moreover, adsorption of two, three, and even four CO molecules is observed, in contrast to RT clusters which at most adsorb one CO molecule. This temperature dependence is related to the lifetime of the cluster-molecule complexes, being much longer for cold clusters. The observed striking size dependence is similar at both temperatures and is discussed in terms of the electronic structure effects.