Effects of O defects on adsorption of small Ag clusterson a MgO(001) surface

The interaction of Ag atoms with a defective MgO(001) surface is systematically studied based on density functional theory. The Ag clusters are deposited on neutral and charged oxygen vacancies of the MgO(001) surface. The structures of Ag clusters take the shape of simple models of two- or three-dimensional (2D and 3D) metal particles deposited on the MgO surface. When the nucleation of the metal clusters occurs in the F_s (missing neutral O) centre, the interaction with the substrate is considerably stronger than that in the F_s⁺ (missing O^- ) centre. The results show that the adsorption of Ag atoms on the MgO surface with oxygen vacancy is stronger than on a clear MgO surface, thereby attracting more Ag atoms to cluster together, and forming atomic islands.     

An ordered surface ternary alloy of a c(6 × 4) structure formed on Cu(0 0 1) by substitutional coadsorption of Mg and Bi

A c(6 × 4) structure formed on Cu(0 0 1) by the coadsorption of Mg and Bi atoms at room temperature has been determined by a tensor low energy electron diffraction analysis. It is an ordered surface ternary alloy with a thickness of single layer, in which Mg, Bi and Cu atoms are mixed in the top layer. In the primitive unit cell, there are one Mg, four Bi, six Cu atoms and one vacancy in the top layer, and substituted Mg and Bi atoms form MgBi₄ plane clusters being arranged in the c(6 × 4) order. Structural parameters show that Mg-Bi bond distances in the MgBi₄ cluster are 3.01 and 3.07 Å, which are shorter than the summation of metallic radii of Mg and Bi. It is concluded that a direct, attractive interaction between Mg and Bi atoms plays critical role in the formation of the c(6 × 4) structure.     

In situ transmission electron microscopy study of the nucleation and grain growth of Ge2Sb2Te5 thin films

The nucleation and grain growth of the Ge₂Sb₂Te₅ (GST) thin films were studied using high voltage electron microscope operated at 1250 kV. As a result, we have found that 2 nm-sized nucleus forms as a cluster which atoms are arranged regularly at the stage of nucleation prior to the formation of grains having crystal structure. The high-resolution transmission electron microscopy study and fast-Fourier transformations revealed that coexistence of face-centered-cubic (FCC) and hexagonal structure occurs, and formation of twin defect is found in the hexagonal structure during the grain growth as the annealing temperature is increased. GST grain having the hexagonal structure grow from the surface, and the growth proceeded perpendicular to the [0 0 0 1], namely the path parallel to the (0 0 0 1) plane. Consequently, grain growth to a large-scale result in a lengthened shape.     

In situ scanning tunneling microscopy studies of bimetallic cluster growth: Pt-Rh on TiO2(1 1 0)

The growth of Pt on clusters on TiO₂(1 1 0) in the presence and absence of Rh was investigated by scanning tunneling microscopy (STM) for Pt deposited on top of 0.3 ML Rh clusters (Rh + Pt). In situ STM studies of Pt growth at room temperature show that bimetallic clusters are produced when Pt is directly incorporated into existing Rh clusters or when newly nucleated clusters of pure Pt coalesce with existing Rh clusters. Low energy ion scattering experiments demonstrate that Rh is still present at the surface of the clusters even after deposition of 2 ML of Pt, indicating that Rh atoms can diffuse to the cluster surface at room temperature. Rh clusters were found to seed the growth of Pt clusters at room temperature as well as 100 K and 450 K. Furthermore, clusters as large as 100 atoms were observed to be mobile on the surface at room temperature and 450 K, but not at 100 K. Pt deposition at 100 K exhibited more two-dimensional cluster growth and higher cluster densities compared to room temperature experiments due to the lower diffusion rate. Increased diffusion rates at 450 K resulted in more three-dimensional cluster growth and lower densities for pure Pt growth, but cluster densities for Pt + Rh growth were the same as at room temperature.     

An investigation of the internal temperature dependence of Pd-Pt cluster beam deposition: A molecular dynamics study

We investigated the internal temperature dependence of the Pd_1−aPt_a cluster beam deposition in the present study via the molecular dynamics simulations of soft-landing. By analysis of the velocity distribution and diffusion coefficient of the bimetallic cluster, Pd atoms with better mobility improved the diffusibility of Pt atoms. The radial composition distribution showed that a Pt-core/Pd-shell structure of the cluster formed at high internal temperatures through migrations of the Pd atoms from inner to surface shells. In the soft-landing process, the diffusing and epitaxial behaviors of the deposited clusters mainly depended on the internal temperature because the incident energy of the cluster was very small. By depositing clusters at high internal temperatures, we obtained a thin film of good epitaxial growth as the energetic cluster impact. Furthermore, nonepitaxial configurations such as scattered nonepitaxial atoms, misoriented particles, and grain boundaries of (1 1 1) planes were produced in the growth of the cluster-assembled film. As the size of the incident cluster increased, the internal temperature of the cluster needed for better interfacial diffusion and contact epitaxy on the substrate also rose.     

Support effects on the nucleation, growth, and morphology of gold nano-clusters

The nucleation, growth, and morphology of gold (Au) clusters on an irreducible oxide (SiO₂), highly reduced TiO_x (x ∼ 1), and less reduced TiO_x (x ∼ 2) were investigated by scanning tunneling microscopy (STM) with the goal of understanding the relationship between the nucleation, growth, and morphology of Au clusters and the reducibility of the oxide support. Au clusters show preferential nucleation and growth on a TiO_x surface compared to a SiO₂ surface. In addition, higher densities of Au clusters were found on highly reduced TiO_x, suggesting that reduced Ti sites play a role as an active site for the nucleation and growth of Au clusters.     

Self-diffusion dynamic behavior of atomic clusters on Re(0 0 0 1) surface

Using molecular dynamics simulations and a modified analytic embedded atom potential, the self-diffusion dynamics of rhenium atomic clusters up to seven atoms on Re(0 0 0 1) surface have been studied in the temperature ranges from 600 K to 1900 K. The simulation time varies from 20 ns to 200 ns according to the cluster sizes and the temperature. The heptamer and trimer are more stable comparing to other neighboring non-compact clusters. The diffusion coefficients of clusters are derived from the mean square displacement of cluster's mass-center, and diffusion prefactors D₀ and activation energies E_a are derived from the Arrhenius relation. It is found that the Arrhenius relation of the adatom can be divided into two parts at different temperature range. The activation energy of clusters increases with the increasing of the atom number in clusters. The prefactor of the heptamer is 2-3 orders of magnitude higher than a usual prefactor because of a large number of nonequivalent diffusion processes. The trimer and heptamer are the nuclei at different temperature range according to the nucleation theory.     

Molecular dynamics study of particle emission by reactive cluster ion impact

Molecular dynamics (MD) simulations of sputtering process with fluorine cluster impact onto silicon targets were performed. By iterating collisional simulations on a same target, accumulation of incident atoms and evolution of surface morphology were examined as well as emission process of precursors. When (F₂)₃₀₀ clusters were sequentially irradiated on Si(1 0 0) target at 6 keV of total incident energy, column-like surface structure covered with F atoms was formed. As the number of incident clusters increased, sputtering yield of Si atoms also increased because the target surface was well fluoridised to provide SiF_x precursors. Size distribution of emitted particles showed that SiF₂ was the major sputtered particle, but various types of silicon-fluoride compounds such like Si₂F_x, Si₃F_x and very large molecules consists of 100 atoms were also observed. This size distribution and kinetic energy distribution of desorbed materials were studied, which showed that the sputtering mechanism with reactive cluster ions is similar to that under thermal equilibrium condition at high-temperature.     

Growth of Rh nanoclusters on TiO2(1 1 0): XPS and LEIS studies

Rhodium clusters were prepared by evaporation on a nearly stoichiometric TiO₂(1 1 0) surface. The growth of metal nanoparticles, as a function of rhodium coverage, could be followed by monitoring the Rh 3d_5/2 XP peak position and by low energy ion scattering spectroscopy (LEIS). The substrate temperature in the 160-300 K regime during evaporation significantly influences the cluster size, leading to smaller crystallites at low temperature. Annealing the surface results in the agglomeration of rhodium, which commenced at lower temperature for smaller clusters. At high temperatures (∼900 K) encapsulation of rhodium also occurred.     

Electronic properties of Au nano-particles supported on stoichiometric and reduced TiO2(1 1 0) substrates

Growth modes and electronic properties were analyzed for Au nano-particles grown on stoichiometric and reduced TiO₂(1 1 0) substrates by medium energy ion scattering (MEIS) and photoelectron spectroscopy(PES) using synchrotron-radiation-light. Initially, two-dimensional islands (2D) with a height of one and two atomic layers grow and higher coverage increases the islands height to form three-dimensional (3D) islands for the stoichiometric TiO₂(1 1 0) substrate. In contrast, 3D islands start to grow from initial stage with a small Au coverage (?0.1 ML, 1 ML = 1.39 × 10¹⁵  atoms/cm²: Au(1 1 1)) probably due to O-vacancies acting as a nucleation site. Above 0.7 ML, all the islands become 3D ones taking a shape of a partial sphere and the Au clusters change to metal for both substrates. We observed the Au 4f and Ti 3p core level shifts together with the valence band spectra. The Ti 3p peak for the O-deficient surface shifts to higher binding energy by 0.25 ± 0.05 eV compared to that for the stoichiometric surface, indicating downward band bending by an electron charge transfer from an O-vacancy induced surface state band to n-type TiO₂ substrate. Higher binding energy shifts of Au 4f peaks observed for both substrates reveal an electron charge transfer from Au to TiO₂ substrates. The work functions of Au nano-particles supported on the stoichiometric and reduced TiO₂ substrates were also determined as a function of Au coverage and explained clearly by the above surface and interface dipoles.     

Thermal and irradiation induced interdiffusion in magnetite thin films grown on magnesium oxide (0 0 1) substrates

Epitaxial Fe₃O₄(0 0 1) thin films (with a thickness in the range of 10-20 nm) grown on MgO substrates were characterized using low-energy electron diffraction (LEED), conversion electron Mössbauer spectroscopy (CEMS) and investigated using Rutherford backscattering spectrometry (RBS), channeling (RBS-C) experiments and X-ray reflectometry (XRR). The Mg out-diffusion from the MgO substrate into the film was observed for the directly-deposited Fe₃O₄/MgO(0 0 1) films. For the Fe₃O₄/Fe/MgO(0 0 1) films, the Mg diffusion was prevented by the Fe layer and the surface layer is always a pure Fe₃O₄ layer. Annealing and ion beam mixing induced a very large interface zone having a spinel and/or wustite formula in the Fe₃O₄-on-Fe film system.     

Mass-selected Ag<Subscript>3</Subscript> clusters soft-landed onto MgO/Mo(100): femtosecond photoemission and first-principles simulations

The electronic structure of supported mass-selected Ag₃ clusters is analyzed by joint femtosecond photoemission spectroscopy and ab initio theoretical investigations. A wide band gap insulating magnesia ultra-thin film on Mo(100) has been chosen as substrate in order to minimize the electronic interaction between metal clusters and support. After magnesia ultra-thin film preparation no photoemission from the molybdenum substrate is observed anymore, instead very weak two photon photoemission is detected possibly originating from surface or subsurface oxide defect states. Soft-landing deposition of 2 of atomic monolayer equivalents of Ag₃ clusters results in the disappearance also of the MgO two photon photoemission signal, while a strong single photon photoemission signal is detected from states located directly below the Fermi level. The theoretical study of structural, electronic and optical properties of Ag₃ at two model sites of MgO (100), the stoichiometric MgO(100) and an F_S-center defect, based on the DFT method and the embedded cluster model provides insight into the interactions between the cluster and the support which are responsible for the characteristic spectroscopic features.     

Density functional theory calculations of surface properties and H2 adsorption on the Cu2O (1 1 1) surface

First-principles calculation on the basis of the density functional theory (DFT) and generalized gradient approximation have been applied to study the adsorption of H₂ on the stoichiometric O-terminated Cu₂O (1 1 1), Cu₂O (1 1 1)-Cu_CUS and Cu-terminated Cu₂O (1 1 1) surfaces. The optimal adsorption position and orientation of H₂ on the stoichiometric O-terminated Cu₂O (1 1 1) surface and Cu-terminated Cu₂O (1 1 1) surface were determined and electronic structural changes upon adsorption were investigated by calculating the Local Density of States (LDOS) of the Cu_CUS 3d and Cu_CUS 4s of stoichiometric O-terminated Cu₂O (1 1 1) surface. These results showed that H₂ molecule adsorption on Cu_CUS site parallel to stoichiometric O-terminated Cu₂O (1 1 1) surface and H₂ molecule adsorption on Cu₂ site parallel to Cu-terminated Cu₂O (1 1 1) surface were the most favored, respectively. The presence of surface copper vacancy has a little influence on the structures when H₂ molecule adsorbs on Cu_CSA, O_CUS and O_CSA atoms and the H₂ molecule is only very weakly bound to the Cu₂O (1 1 1)-Cu_CUS surface. From the analysis of stoichiometric O-terminated Cu₂O (1 1 1) Local Density of States, it is observed that Cu_CUS 3d orbital has moved to a lower energy and the sharp band of Cu_CUS 4s is delocalized when compared to that before H₂ molecule adsorption, and overlapped substantially with bands due to adsorbed H₂ molecule. The Mulliken charges of H₂ adsorption on Cu_CUS site showed that H₂ molecule obtained electron from Cu_CUS which was consistent with the calculated electronic structural changes upon H₂ adsorption.     

Yields and ionization probabilities of sputtered Inn particles under atomic and polyatomic Aum ion bombardment

The emission of neutral and charged atoms and clusters from a polycrystalline indium surface under bombardment with 5 and 10 keV Au, Au₂, Au₃ and Au₅ projectiles was investigated. Single photon laser postionization was utilized for the detection of sputtered neutral particles. Secondary ions were detected without the laser under otherwise exactly the same experimental conditions. The relative cluster yields were found to be enhanced under polyatomic projectile bombardment, more so the larger the number of atoms in the sputtered cluster. The ionization probability strongly increases with increasing cluster size, but is essentially independent of the projectile impact energy. At a fixed impact energy, the ionization probability of sputtered monomers was found to decrease with increasing number of constituent gold atoms per projectile, but there was no detectable effect for sputtered dimers and larger clusters.     

First-principles studies on initial growth of Ni on MgO(0 0 1) surface

To elucidate the initial growth of metal on oxide surface, we studied adsorption of small nickel clusters, Ni_n (n = 1-5), on MgO(0 0 1) surface using first-principles method based on density-functional theory. It was found that the preferential adsorption site for an isolated Ni atom is directly above the surface oxygen atom. A strong covalent bond with partial ionic character is formed between the Ni adatom and the surface oxygen atom. Various structures were considered for the Ni_n isomers and 3D structures were found to be energetically more stable than 2D structures for clusters of more than two atoms. For the 2D clusters, metal-metal bonds prevail over metal-substrate bonds with increasing Ni coverage. The calculated work function and ionization energy were found to vary with Ni coverage which is attributed to the change of the surface dipole moment upon metal adsorption, while the evolution of Schottky barrier height at the initial growth stage is dominated by the adatom-induced gap states.     

Charging and stabilization of Pd atoms and clusters on an electron-rich MgO surface

We report density functional theory calculations on the interaction of Pd atoms and small Pd clusters with an electron-rich MgO surface. This surface can be generated by forming a specific kind of defects, named (H⁺)(e⁻) centers, using well known chemical recipes. By deposition of gas-phase Pd atoms on the properly functionalized MgO surface, one can generate collections of small Pd cluster anions with peculiar chemical properties. The (H⁺)(e⁻) centers act as nucleation sites for diffusing Pd atoms and favor the formation of small, thermally stable clusters. The presence of an extra charge on the metal cluster results in a large vibrational red-shift of adsorbed CO molecules. The present results intend to stimulate experimental work to produce stable metal cluster anions on the surface of an ionic oxide.     

Optical properties of small silver clusters supported at MgO

We present structural and optical properties of silver clusters Ag_n (n=2, 4, 6, 8) at two model support sites of MgO, stoichiometric MgO(100) and F_S-center defect, based on density functional theory and embedded cluster model. Our results provide the mechanism responsible for the absorption and emission patterns due to the specific interaction between the excitations within the cluster and the support site which is strongly cluster size and structure dependent. We propose Ag₄ at stoichiometric site as well as Ag₂, Ag₄ and Ag₆ at F_S-center defects as good candidates for the emissive centers in the visible regime.     

Nucleation of ordered Fe islands on Al2O3/Ni3Al(1 1 1)

Scanning tunneling microscopy (STM) has been used to investigate the nucleation and stability of iron clusters on the Al₂O₃/Ni₃Al(1 1 1) surface as a function of coverage and annealing temperature. We show that atomic beam deposition of iron leads to hexagonally ordered cluster arrangements with a distance of 24 Å between the clusters evidencing the template effect of the alumina film. The shape of the iron clusters is two-dimensional (2D) at deposition temperatures from 130 K to 160 K and three-dimensional (3D) at 300 K. However, the 2D iron clusters grown between 130 K and 160 K are stable up to 350 K.     

Combined Rietveld refinement of BaMgAl10O17:Eu using X-ray and neutron powder diffraction data

The phosphor, BaMgAl₁₀O₁₇:Eu²⁺, showing a blue emission band at about 450 nm was prepared by a normal solid-state reaction using BaCO₃, Al₂O₃, MgO and Eu₂O₃ as starting materials with AlF₃ as a flux. The study of combined Rietveld refinement and photoluminescence spectra was carried out to determine the structural parameters, such as lattice constants, the valence state of Eu, the site preference of Mg and site fractions of Mg and Eu. The occupancies of Eu and Mg were 0.022 and 0.526, respectively. The valence state of Eu was the divalent state because there was only one broad line at about 450 nm in the photoluminescence spectrum. The site preference of Mg atoms was the tetrahedral site of Al atoms surrounded by oxygen atoms in the spinel block. Lattice parameters decreased due to the difference of two ionic radii, Eu²⁺(1.09 Å) and Ba²⁺(1.34 Å), compared with those of BaMgAl₁₀O₁₇.     

Formation and stabilization of Fe-induced magic clusters on Si(1 1 1)-(7 × 7) template

We demonstrate the growth of Fe-induced magic clusters on Si(1 1 1)-(7 × 7) template by in situ scanning tunneling microscopy (STM). These clusters form near a dimer row at one side of the half-unit cell (HUC); and with three different equivalent orientations. A cluster model comprising three top layer Si atoms bonded to six Fe atoms at the next layer in the 7 × 7 faulted-half template is proposed. The optimized cluster structure determined by first-principles total-energy calculation shows an inward-shifting of the three center Fe atoms. The clusters and the nearby center-adatoms of the next HUCs appear with a significantly reduced height below bias voltages 0.4 V in high resolution empty-state STM images, suggesting an energy gap opening near the Fermi level at these localized cluster and adatom sites. We explain the stabilization of the clusters on the 7 × 7 template using the gain in electronic energy as the driving force for cluster formation.