镍单晶膜上氧化镍的配位生长取向关系

对在膜面为(110),(001)和(111)的镍单晶膜上生成的氧化镍取向进行了电子衍射分析,除在(111)和(001)镍膜上肯定了前人已发现的氧化镍与镍的平行取向关系外,还在(110)和(001)镍单晶膜上发现了(111)_NiO∥(001)_Ni,〈110〉_NiO∥〈110〉_Ni取向关系以及〈110〉_NiO∥〈110〉_Ni氧化镍纤维织构。在所有氧化镍与镍的取向关系中均有〈110     

Probing Single Nanometer-scale Particles with Scanning Tunneling Microscopy and Spectroscopies

Scanning tunneling microscopy can be used to isolate single particles on surfaces for further study. Local optical and electronic properties coupled with topographic information collected by the scanning tunneling microscope (STM) give insight into the intrinsic properties of the species under study. Since each spectroscopic measurement is done on a single particle, each sample is monodisperse, regardless of the degree of heterogeneity of the original preparation. We illustrate this with three example systems – a metal cluster of known atomic structure, metal nanoparticles dispersed from colloid suspensions, and metallocarbohedrenes (Met-Cars) deposited with other reaction products. Au and Ag nanoparticles were imaged using a photon emission STM. The threshold voltage, the lowest bias voltage at which photons are produced, was determined for Au nanoparticles. Electronic spectra of small clusters of Ni atoms on MoS₂ were recorded. Preliminary images of Zr-based Met-Car-containing soot were obtained on Au and MoS₂ substrates and partial electronic spectra were recorded of these possible Met-Car particles.     

Si3N4/Si表面Si生长过程的扫描隧道显微镜研究

利用原位扫描隧道显微镜和低能电子衍射分析了Si的纳米颗粒在Si₃N₄/Si(111)和Si₃N₄/Si(100)表面生长过程的结构演变.在生长早期T为350—1075K范围内,Si在两种衬底表面上都形成高密度的三维纳米团簇,这些团簇的大小均在几个纳米范围内,并且在高温退火时保持相当稳定的形状而不相互融合.当生长继续时,Si的晶体小面开始显现.在晶态的Si₃N₄(0001)/S 关键词： 氮化硅 扫描隧道显微镜 纳米颗粒     

Structure of graphene on the Ni(110) surface

The structure of graphene on Ni(110) was studied using scanning tunneling microscopy (STM) and low-energy electron diffraction spectroscopy. STM images show a Moire structure, depending on the orientation of the domains making up the graphene layer. A simple model has been proposed which permits prediction of the Moire structure and interpretation of STM images based on calculation of the distances between the nearest neighbor carbon and nickel atoms. Our theoretical calculation suggests that the final orientation of graphene domains forming in the course of synthesis is defined by the angle of rotation of small clusters in the initial stages of growth.     

Fundamental processes in Si/Si and Ge/Si epitaxy studied by scanning tunneling microscopy during growth

Experimental results on the epitaxy of Si and Ge on Si(0 0 1) and Si(1 1 1) surfaces, which are obtained by scanning tunneling microscopy (STM) imaging during growth, are reviewed. Techniques for simultaneous epitaxial growth and STM measurements at high temperature are described. The ability to access the evolution of the growth morphology during growth down to the atomic level enables the study of the influence of surface reconstruction on the growth. The relatively complete characterization of the growth process facilitates comparison to theoretical models and allows the identification of fundamental growth processes. For instance, the observed transition between different growth modes can be explained by specific growth processes included in a model. The influence of strain on the growth morphology is reviewed for the case of heteroepitaxial growth of Ge on Si. With the method of combining STM imaging and epitaxial growth, the transition from two-dimensional to three-dimensional growth as well as the evolution of size and shape of three-dimensional islands can be studied.     

Ethylene dissociation on flat and stepped Ni(1 1 1): A combined STM and DFT study

The dissociative adsorption of ethylene (C₂H₄) on Ni(1 1 1) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (1 1 1) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges.DFT calculations were performed for several intermediate steps in the decomposition of ethylene on both Ni(1 1 1) and the stepped Ni(2 1 1) surface. In general the Ni(2 1 1) surface is found to have a higher reactivity than the Ni(1 1 1) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular the barrier for dissociation is lowered significantly more than the barrier for dehydrogenation, and this is of great importance for the bond-breaking selectivity of Ni surfaces.The influence of step edges was also probed by evaporating Ag onto the Ni(1 1 1) surface. STM shows that the room temperature evaporation leads to a step flow growth of Ag islands, and a subsequent annealing at 800 K causes the Ag atoms to completely wet the step edges of Ni(1 1 1). The blocking of the step edges is shown to prevent all decomposition of ethylene at room temperature, whereas the terrace site decomposition at 500 K is confirmed to be unaffected by the Ag atoms.Finally a high surface area NiAg alloy catalyst supported on MgAl₂O₄ was synthesized and tested in flow reactor measurements. The NiAg catalyst has a much lower activity for ethane hydrogenolysis than a similar Ni catalyst, which can be rationalized by the STM and DFT results.     

Atomic-scale surface science phenomena studied by scanning tunneling microscopy

Following the development of the scanning tunneling microscope (STM), the technique has become a very powerful and important tool for the field of surface science, since it provides direct real-space imaging of single atoms, molecules and adsorbate structures on surfaces. From a fundamental perspective, the STM has changed many basic conceptions about surfaces, and paved the way for a markedly better understanding of atomic-scale phenomena on surfaces, in particular in elucidating the importance of local bonding geometries, defects and resolving non-periodic structures and complex co-existing phases. The so-called “surface science approach”, where a complex system is reduced to its basic components and studied under well-controlled conditions, has been used successfully in combination with STM to study various fundamental phenomena relevant to the properties of surfaces in technological applications such as heterogeneous catalysis, tribology, sensors or medical implants. In this tribute edition to Gerhard Ertl, we highlight a few examples from the STM group at the University of Aarhus, where STM studies have revealed the unique role of surface defects for the stability and dispersion of Au nanoclusters on TiO₂, the nature of the catalytically active edge sites on MoS₂ nanoclusters and the catalytic properties of Au/Ni or Ag/Ni surfaces. Finally, we briefly review how reaction between complex organic molecules can be used to device new methods for self-organisation of molecular surface structures joined by comparatively strong covalent bonds.     

Structural and electronic properties of thin Ni layers on Cu(1 1 1) as investigated by ARPES, STM and GIXD

The growth and the crystalline and electronic structure of Ni deposited on single crystalline Cu(1 1 1) were studied by scanning tunnelling microscopy (STM), grazing incidence X-ray diffraction (GIXD) and angle-resolved photoemission spectroscopy (ARPES). In the early stages of growth monoatomic-high flat Ni islands, partially covered by Cu migrating from the surface, are observed. Starting from a pseudomorphic epitaxial relationship the in-plane lattice parameter progressively relaxes with increasing coverage. For a 20 monolayer (ML) thick deposit the in-plane lattice parameter is still found halfway between the bulk Ni and Cu lattice parameters. ARPES data also rule out the layer-by-layer growth and provide the values of the Ni exchange splitting.     

Exchange bias in structure-phase separated K0.8Fe2−xNixSe2 (x=0.015) single crystal: Interface evidence

Exchange bias behavior is observed in Ni slightly doped K_0.8Fe_2−xNi_xSe₂ (x=0.015) single crystal. Two distinguished phases with epitaxial growth were observed in X-ray diffraction experiments, indicating the structure phase separation in our samples. The magnetic hysteresis loop shifts in both horizontal and vertical directions when the sample was cooled down to 3 K in a magnetic field. The nature of this magnetic anisotropy could be understood as a result of the freezing properties of the local spin disorders in cluster like spin-glass system. Our results suggest that the sample contains short range weak ferromagnetic clusters (phase 2) embedding in the antiferromagnetic backgrounds (phase 1), in which the random distribution of Ni on Fe or Fe-vacancy sites quenched the superconductivity and induced spin disorders.     

The passivation of atomic scale defects present on III–V semiconductor laser facets: an STM/STS investigation

The work presented in this paper is based on the use of scanning tunnelling microscopy (STM) and scanning tunnelling spectroscopy (STS) to study the passivation of atomic scale defect-induced surface states on cleaved III–V (1 1 0) surfaces. This is based on the use of thin Si layers deposited in situ on to the atomically clean surface. The simultaneous STM and STS measurements allowed direct correlation of the structural and electronic properties at the nanoscopic level. The preferential adsorption of Si clusters onto surface defects was achieved using elevated temperature growth on the GaAs(1 1 0) substrate. The STS results clearly indicated local electronic passivation of both step defects and vacancy clusters when the interface is formed at 280 °C. This observation was also confirmed on a macroscopic level using X-ray photoelectron spectroscopy (XPS) under identical conditions. The results are interpreted in terms of the surface bonding of Si with the defect sites. Furthermore, this STM/STS study has been extended to real laser devices where comparable defect features are observed. The implications of defect passivation in nanotechnology are also discussed.     

Three-Ni-atom cluster formed by sulfur adsorption on Ni(1 1 1)

Sulfur adsorption on Ni(1 1 1) at room temperature has been studied by scanning tunneling microscopy. Irregularly-shaped islands, which are aggregates of small particles, appear with troughs on (1 1 1) terraces. Estimating the number of small particles in the irregular islands and that of Ni atoms ejected through the formation of troughs, we find that each small particle contains three Ni atoms. A three-Ni-atom cluster is proposed, where three S atoms are adsorbed on 4-fold hollow sites formed on the sides of the cluster. The Ni₃S₃ cluster can assume two orientations on the (1 1 1) surface. We show that the apparently-irregular distribution of small particles is well understood by assuming the alternate orientation of neighboring Ni₃S₃ clusters and the slight energy difference between the two orientations of a single Ni₃S₃ cluster. Real-time observation of a Ni(1 1 1) surface under H₂S ambience reveals that small islands composed of three or four Ni₃S₃ clusters change their positions rapidly, preventing the simple growth of islands at the initially-nucleated positions.     

Growth of fcc(111) on bcc(110): Influence of growth and annealing temperature on epitaxy and surface morphology for Pd on Cr

The effects of growth versus annealing temperature on epitaxial relationship and surface morphology were studied for Pd(111) films on Cr(110) surfaces. While the epitaxial orientation of the Pd films depends on film thickness as well as on growth temperature, subsequent annealing has no effect on the epitaxial orientation. Instead, additional annealing of room temperature grown films takes the surface morphology from an island to a terrace shape, which was not observed for samples directly grown at elevated temperatures. These different effects that growth and annealing temperature have, help understanding the resulting structure and morphology of the heteroepitaxial system.     

Characterization of epitaxial MgO growth on Si(001) surface

MgO epitaxial growth on a Si(001) surface by ultrahigh-vacuum molecular beam epitaxy was investigated. Epitaxial orientation and crystalline quality were characterized based on the three-dimensional reciprocal map obtained by Weissenberg RHEED. The epitaxial orientation and crystallinity were strongly dependent on the initial condition of the substrate. When MgO was deposited on a clean Si(001) surface at room temperature a MgO(001) film grew on the Si(001) substrate with two in-plane orientations:MgO[110]//Si[100] and MgO[100]//Si[100]. This is the first observation of MgO epitaxy with the former orientation, which has a smaller mismatch than the latter orientation. When the substrate was exposed to O₂ or thermally oxidized, the latterorientation predominantly grew on the substrate. Deposition of Mg on the substrate also produced the latter orientation. These results imply that nucleation sites on the initial substrate play an important role in determining the epitaxial orientation.     

Solid-state synthesis in Ni/Fe/MgO(001) epitaxial thin films

Solid-state synthesis in Ni/Fe/MgO(001) bilayer epitaxial thin films has been studied experimentally. The phase sequence Fe/Ni→(～350°C)Ni₃Fe→(～400°C)NiFe→(～ 550°C)γ_par is formed as the annealing temperature increases. The crystal structure in the invar region consists of epitaxially intergrown single-crystal blocks consisting of the paramagnetic γ_par and ferromagnetic NiFe phases, which satisfy the orientation relationship [100](001)NiFe ∥ [100](001) γ_par. It has been shown that the nucleation temperatures of the Ni₃Fe, NiFe, and γ_par phases coincide with the temperatures of solid-state transformations in the Ni-Fe system.     

Measuring the implantation depth of silver clusters in graphite

Scanning tunnelling microscopy (STM) and molecular dynamics (MD) simulations have been used to investigate the implantation of Ag₇ ^- clusters into the graphite surface. An experimental measure of the implantation depth of individual clusters is gained via thermal oxidation of the bombarded graphite surfaces. This process results in etching of the cluster-induced defects to form etch pits which grow laterally whilst retaining the depth of the implanted cluster. STM imaging of the etch pits reveals the distribution of implantation depths for deposition energies of 2 keV and 5 keV. Molecular dynamics simulations for clusters of 5 keV energy show that the implantation depth for Ag₇ ^- is largely independent of the impact site on the graphite surface and the cluster orientation. The implantation depth found by MD lies at the upper edge of the experimental depth distribution. Received 30 November 2000     

Ni(CO)4 formation on single Ni crystals: Reaction kinetics and observation of surface facetting induced by the reaction

We have studied the kinetics of the synthesis of nickel carbonyl (Ni + 4 CO → Ni(CO)₄), using single crystalline Ni surfaces of different crystallographic orientation. A dependence of the reaction rate on the crystallographic orientation of the surface has been observed. Scanning electron micrographs showed that a very sharp (111) facetting of the surface takes place during the reaction. A reaction mechanism for the Ni(CO)₄ formation, taking into account recent experimental data of the chemisorption of CO on Ni, is discussed, which may explain the kinetic results and the observed facetting.     

Binding energy shift in photoemission spectroscopy study of Ni clusters deposited on rutile TiO2 surfaces

Cluster-size-dependent binding energy (BE) shifts of Ni 2p_3/2 spectra in Ni clusters with respect to bulk Ni metal have been studied as a function of Ni coverage on clean rutile TiO₂(0 0 1) surfaces at room temperature. Auger parameter (AP) analysis of photoelectron spectra has been employed and revealed an obvious initial state contribution at the coverage of 0.5 monolayers (ML). The initial state effect was demonstrated to be strongly affected by the substrate and was assigned to a combination of eigenvalue shift in surface core-level shift (SCLS) and charge transfer between the metal clusters and substrates. The TiO₂(0 0 1) surface stoichiometry was found to introduce different charge transfer behaviors. Our results experimentally present that the Ni clusters are charged positively on stoichiomtric TiO₂ surface and less positively or even negatively on various reduced surfaces.     

Growth and characterization of Au,Ni and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh

The nucleation and thermal stability of Au, Ni, and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh as well as the interaction between Au–Ni bimetallic clusters and reactive gases have been studied by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Both Au and Ni atoms grow as three-dimensional (3D) clusters. Annealing the Au/carbon nanomesh surface up to 1150 °C leads to complete desorption of the Au clusters, while interfacial reaction occurs between Ni clusters and the substrate surface when the Ni clusters are subjected to the same annealing process. The nucleation of Au–Ni clusters depends critically on the deposition sequence. Au atoms preferentially nucleate on the existing Ni clusters, leading to the formation of bimetallic clusters with Au enriched on the surface. If the deposition sequence is reversed, a part of Ni atoms nucleate between the Au clusters. The thermal stability of the Au–Ni clusters resembles that of the Ni/carbon nanomesh surface, irrespective of the deposition sequence. XPS characterization reveals that Ni atoms in Au–Ni bimetallic clusters are oxidized upon exposure to 5.0 × 10^? 7 mbar O₂ for 5 min at room temperature while negligible structure change can be detected when the bimetallic clusters are exposed to CO gas under the similar conditions.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.