Exchange processes in interlayer diffusion – kinks, corners and the growth mode

Interlayer diffusion, i.e. mass transport between different terraces, is known to be an essential process for obtaining layer-by-layer growth, avoiding formation of three-dimensional (3D) islands when growing thin films. We present experimental results for the growth of cobalt on Pt (111), which demonstrate the importance of kinks and corners for interlayer diffusion. We show that Co grows two-dimensionally as long as strain caused by the Pt-Co interface keeps the step edges rough, with a high kink density, and then transforms to 3D growth with straight steps. The results for growth with adsorbed carbon monoxide show that CO acts as a surfactant, causing two-dimensional growth unless heterogeneous nucleation occurs. Again, this process is related to roughening of the steps, being a new mechanism for the action of a surfactant. A scanning tunneling microscopy study at the atomic scale confirms the fact that step descent happens only at kinks and (concave) corners, and in conjunction with simulations allows us to identify some of the relevant atomic-exchange processes. We finally argue that the dependence of the growth mode on the step morphology, together with straightening of the steps by step–step interaction, can lead to an instability of the growth mode. Received: 27 March 2000 / Accepted: 4 September 2000 / Published online: 7 March 2001     

Steps,facets and nanostructures: investigations of Cu (11n) surfaces

Step structure and dynamics and adsorbate-induced reconstruction of stepped surfaces are useful features for investigating fundamental surface phenomena and their practical consequences. In this respect, vicinal Cu (11n) surfaces with n=3, 5 and 9 were studied by scanning tunneling microscopy (STM) at 300 K. While the regular monoatomic steps fluctuate for Cu (119), they are apparently stabilized for n≤5 by their strong repulsive interaction and this leads to a very low kink activity. In addition to the regular steps, the formation of double steps was observed as a particular phenomenon on those surfaces. These double steps determine the dynamic behavior at room temperature. By applying existing models for the fluctuations of the step positions in space and time, the formation energy for kinks at these double steps was determined to be 0.16 eV for Cu (115). According to this evaluation, diffusion along step edges is the dominating mass-transport mechanism. A model for the structure of the double steps and for the atomic displacement processes necessary for kink migration at these steps is presented. Complete faceting is observed for these surfaces upon oxygen adsorption at elevated temperatures (around 500 K) and was studied in detail for n=5 and 9. Both surfaces reconstruct into two types of {104} facets and a third facet, the orientation of which is determined by the macroscopic crystal orientation. The facet size is governed by the formation kinetics and can be controlled by varying the crystal temperature or the oxygen partial pressure. The formation kinetics is discussed as a nucleation and growth process and the relevant parameters are given. Facets within a range of size between 5 nm and 100 nm could thus be produced. They remained stable at ambient atmosphere, up to about 620 K, and also if covered by additional metal layers such as Ni. Received: 1 June 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Promotors,poisons and surfactants: Electronic effects of surface doping on metals

The interaction of adsorbates with metal surfaces is discussed. It is shown that the evanescent charge density produced by occupied sp derived surface states yields a considerable contribution to the Pauli repulsion experienced by adsorbate particles with a closed-shell electronic structure, e.g. rare-gases or molecules such as H₂ or N₂. For rare-gases this results in a reduction of the binding energy in the presence of occupied surface states, for molecules this gives rise to an additional contribution to the dissociation barrier. Suitable surface dopants are able to depopulate surface states and thereby to reduce the dissociation barrier. Such dopants can substantially promote catalytic reactions in which the dissociation from the gas phase or a physisorbed precursor is the rate limiting step. In contrast to closed-shell systems the bonding interaction for metal adsorbates on metal substrates is enhanced by occupied surface states. This leads to an extra diffusion barrier at steps, because the surface state amplitude drops to zero at upper step edges. The additional step-edge barrier, which is a kinetic hindrance for layer-by-layer growth, can be reduced by surface dopants depopulating the corresponding surface state. Such dopants promote layer-by-layer growth and act therefore as surfactants. It is concluded that the effect of promoters in catalysis and of surfactants in metal epitaxy is in part due to the same basic mechanism, namely the depopulation of surface states.     

Atom manipulation with the scanning tunneling microscope: nanostructuring and femtochemistry

We briefly survey our recent studies on the ‘soft’lateral manipulation of atoms and small molecules with the scanning tunneling microscope (STM), whereby mainly the tip–surface forces are employed. Repulsive (pushing) as well as discontinuous (pulling) and continuous (sliding)attractive manipulation modes could be distinguished on Cu(211) for CO molecules and metal atoms, respectively. In the case of pulling of Cu atoms on Cu(111) even finer details could be discerned: the adparticle may show various movement patterns visiting different surface sites upon applying different tip forces. Lateral manipulation also allows modifications of the Cu(211) substrate itself in an atom-by-atom manner by releasing atoms from sixfold coordinated kink sites and even sevenfold coordinated regular step sites. Furthermore, investigations concerning controled vertical manipulation with emphasis on ‘picking-up’ single CO molecules are reported. The mechanism behind vertical transfer of CO molecules relates to ultrafast chemical processes. Vertical manipulation implies, besides extending the possibilities for the build-up of nanostructures, the important possibility of creating structurally and compositionally well-defined tips, which may eventually lead to chemical sensitivity with the STM.     

Near molecular-scale growth of natural minerals: Experimental methods and errors in length-dependent step speeds with scanning probe microscopy

Experimental observation of step (i.e., a linear discontinuity in a surface) growth on calcium carbonate and barium sulfate surfaces was performed using in situ scanning probe microscopy (SPM) in aqueous solutions. Step speeds at very short step lengths (<300 nm) were found to increase with step length, but scatter in the data precluded comparison of different theoretical models with regard to the experimental data. Analysis of experimental errors revealed that the data scatter was not unusual and further suggested that significant experimental bias in the determination of step properties such as the step free energy and kinetics of kink propagation and nucleation are introduced if the instrument bandwidth is not appropriate for the specific dynamics of the step. In light of step growth models based on either equilibrium assumptions or non-equilibrium assumptions, these biases tend to favor one model over the other.     

Instability of vicinal crystal surfaces with transparent steps: Transient kinetics and non-local electromigration

The steps at the crystal surfaces could be partially transparent in the sense that the migrating adatoms can cross the steps without visiting a kink position. In the case of significant transparency the velocity of a given step in a given moment is affected by atomic processes which took place at rather distant terraces in rather earlier moments. The reason is that an adatom needs time to cross many terraces before attaching to a kink position. That is why the theory of crystallization with non-local kinetics should account for the time dependence of the adatom concentrations on the terraces. Such a transient growth model (going beyond the quasi-static approximation of the BCF theory of crystal growth) is developed here for the limit of slow kinetics at the steps and fast surface diffusion. This model predicts instability of the vicinal surface (in agreement with the earlier studies) but rather different expression for the wavelength of the most unstable mode, which depends only on the ratio between the step transparency and the step kinetic coefficients.     

Kinetics and thermodynamics of sucrose crystal growth in the presence of a non-ionic surfactant

Batch experiments were carried out to study the effect of Hodag CB6, a non-ionic surfactant, on the growth kinetics of sucrose crystals as a function of supersaturation, impurity concentration and temperature. The growth promoting effect of the added impurity, studied using a recently introduced spiral nucleation model (SNM), was due to the decrease in the surface free energy induced by the added surfactant. The growth process was influenced by both kinetic and thermodynamic effect, the latter being predominant. The coverage of impurity molecules on the sucrose surface followed a Henry type expression according to Langmuir isotherm at studied temperatures. In the case of a pure system, the total active kink density was found to be around 10¹⁶ kinks/m². The active growth sites on the crystal surface were found to be two orders of magnitude lower than the total number of sucrose molecules.     

Molecular dynamics simulations of electrostatic layer-by-layer self-assembly

Electrostatic assembly of multilayered thin films through sequential adsorption of polyions in layer-by-layer fashion utilizes the strong electrostatic attraction between oppositely charged molecules. We perform molecular dynamics simulations of multilayers of flexible polyelectrolytes around a charged spherical particle. Our simulations establish that the charge reversal after each deposition step is a crucial factor for the steady layer growth. The multilayers appear to be nonequilibrium structures.     

Modeling soot formation in flames and reactors: Recent progress and current challenges

The study of soot has long been motivated by its adverse impacts on health and the environment. However, this combustion knowledge is also relevant to the production of carbon black and hydrogen via methane pyrolysis which are important commodities. Over the last decade, steady progress has been made in the development of detailed continuum models of soot formation in flames and reactors. Developing more comprehensive models has often been motivated by the need for predicting soot formation over a wider range of conditions (e.g., temperature, pressure, fuels). Measurements with novel experimental techniques have given us new insights into the chemistry, particle dynamics and optical properties of soot particles and even molecules and radicals forming them. Also, multi-scale modeling has enabled us to translate the detailed mechanisms of soot processes based on first principles into computationally efficient but accurate continuum models of soot formation in flames and reactors. However, important questions remain including (1) what is the mechanism of soot inception and surface growth, (2) which gas-phase species are involved in soot inception and surface growth (3) how surface growth and oxidation are affected by soot surface properties. Proposed models need to be evaluated against experimental data over a wide range of conditions to determine their predictive strength. These questions are critical for the accurate prediction of soot formation in flames and its emissions from engines. However, this knowledge can also be used to develop predictive process design and optimization tools for carbon black and other nanocarbon formation in reactors.     

Mixing length scales: step meandering and island nucleation on vicinal surfaces

Simultaneous island nucleation and step flow growth on vicinal surfaces are studied by Monte Carlo simulations. Step edges experience meandering instability under growth conditions if there is a kink barrier suppressing adatom jumps around kink sites. This instability has a characteristic length scale, with different scaling properties from the island separation scale. We show that there is a coupling between island nucleation and step edge instability. The length scale associated with nucleation begins to couple with the wavelength of the step edge patterns when islands and steps coalesce. Only in the submonolayer regime step meandering is independent of island formation. In this regime the island separation has a cross-over scaling behaviour as terrace width is varied.Received: 9 April 2003, Published online: 19 November 2003PACS: 81.15.Aa Theory and models of film growth - 68.55.Ac Nucleation and growth: microscopic aspects - 81.16.Rf Nanoscale pattern formationM. Rusanen: Present address: Institut Français du Pétrole, Groupe de Modélisation Moléculaire, BP 311, 92852 Rueil-Malmaison, FranceJ. Kallunki: Present address: Laboratory of Physics, PO Box 1100, FIN-02015 HUT, Espoo, Finland     

Time-resolved observation of CVD-growth of silicon on Si(111) with STM

Scanning tunneling microscopy is used to study the epitaxial growth of silicon on Si(111)-(7×7) by Chemical Vapour Deposition (CVD) of disilane (Si₂H₆) at elevated substrate temperatures directly during the growth process. Different kinetic processes, as island nucleation, growth and coarsening and step flow have directly been imaged as a function of temperature and Si₂H₆ flow. On a substrate with a low defect concentration several growth modes depending on the flux and the total coverage are distinguished: the formation of multi-level islands as a transient mode leaving the substrate partially uncovered up to 20 bilayers, a transition to layer-by-layer growth when the multi-level islands initially formed coalesce and the formation of three-dimensional islands with tetrahedral shape at higher growth rates which are only metastable due to the presence of hydrogen at the surface. The equilibrium shape of two-dimensional islands is a hexagon whereas the kinetically influenced shape during growth is triangular.     

Instability and wavelength selection during step flow growth of metal surfaces vicinal to fcc(001)

We study the onset and development of ledge instabilities during growth of vicinal metal surfaces using kinetic Monte Carlo simulations. We observe the formation of periodic patterns at [110] close packed step edges on surfaces vicinal to fcc(001) under realistic molecular beam epitaxy conditions. The corresponding wavelength and its temperature dependence are studied in detail. Simulations suggest that the ledge instability on fcc(1,1,m) vicinal surfaces is controlled by the strong kink Ehrlich-Schwoebel barrier, with the wavelength determined by dimer nucleation at the step edge. Our results are in agreement with recent continuum theoretical predictions, and experiments on Cu(1,1,17) vicinal surfaces.     

Surface roughening by anisotropic adatom kinetics in epitaxial growth of La0.67Ca0.33MnO3

The growth mechanisms and surface morphology of colossal magnetoresistance (CMR) La_0.67Ca_0.33MnO₃ films deposited by rf magnetron sputtering on SrTiO₃(0 0 1) substrates are investigated. The films are epitaxial, coherently strained and ferromagnetic. It is found that at early growth stages, in nanometric films, a layer-by-layer mechanism dominates, which results in step and terrace surface morphology. Upon further growth, the flat surface becomes unstable when large two-dimensional (2D) islands form. The Erlich-Schwoebel step-edge energy barrier induces an anisotropic adatom kinetics that favors 2D nucleation on top of the islands as it reduces downhill adatom current. As a result, there is an evolution with growth to mound-like structures of increasing height. Critical thickness for mound formation and average mound separation can be tuned by substrate miscut angle and growth temperature. These results provide a detailed understanding of the roughening process in manganites and are relevant for the controlled fabrication of CMR films, in particular for its use in epitaxial heterostructures.     

Energetics of the growth mode transition in InAs/GaAs(0 0 1) small quantum dot formation: A first-principles study

Based on first-principles density-functional pseudopotential calculations, the growth of InAs on the GaAs(0 0 1) surface has been studied. By analyzing the free energies of the surfaces with different thicknesses of the InAs coverages, the critical thickness of the layer-by-layer (2D) to island (3D) growth mode transition is predicted to be around 1.5 ML. Comparing the total energy differences between layer-by-layer growth models and 3D island models, the mechanism of the 2D-3D growth mode transition near the critical thickness (θ_crit) is studied which indicates that at the initial stage of InAs quantum dots formation, small 3D islands are formed randomly.     

Structure and polarity of 8CB films evaporated onto solid substrates

Brewster-angle reflection ellipsometry and surface optical second harmonic generation were used to study the growth of 4'-n-octyl-4-cyanobiphenyl (8CB) films evaporated in air onto polymeric and quartz glass substrates. The layer-by-layer growth of the films terminates after formation of two distinctive interfacial layers. Both of these two layers are polar and tilted. In the first layer the molecules lie nearly flat on the surface, while in the second layer they point on average about 50° toward the surface normal. The dipole moment of the second layer has a lower magnitude and an opposite direction with respect to the dipole moment of the first layer.     

拉曼光谱和DSC研究人参皂苷分子与DMPC双层膜的作用

探讨药物与细胞膜的作用对于改善药物的药理活性、揭示药物的作用机制具有重要意义。利用差示扫描量热(DSC)和拉曼光谱技术对五种人参皂苷分子与DMPC磷脂双层膜的作用进行了实验研究。结果显示,在人参皂苷分子的作用下,DMPC的极性头部骨架构象没有发生变化。Rb1和Rh2增多了脂肪酰链中无序性的构象,增强了侧链排列的无序性,而三醇组皂苷Re,Rf和Rg1对DMPC双层膜的影响较小。DSC结果进一步表明,Rb1和Rh2均与DMPC双层膜发生了强相互作用,两皂苷分子使DMPC的相变温度显著降低,双层膜的流动性增强。Rf对DMPC双层膜的扰动作用要强于Re和Rg1。     

Terminating surface electromigration at the source

Based on an extensive search across the periodic table utilizing first-principles density functional theory, we discover phosphorus to be an optimal surface electromigration inhibitor on the technologically important Cu(111) surface--the dominant diffusion pathway in modern nanoelectronics interconnects. Unrecognized thus far, such an inhibitor is characterized by energetically favoring (and binding strongly at) the kink sites of step edges. These properties are determined to generally reside in elements that form strong covalent bonds with substrate metal atoms. This finding sheds new light on the possibility of halting surface electromigration via kink blocking impurities.     

Direct Synthesis of ZIF-8 on Transmission Electron Microscopy Grids Allows Structure Analysis and 3D Reconstruction

The first example of layer-by-layer growth of a metal–organic framework (MOF) directly on transmission electron microscopy (TEM) grids is described. ZIF-8 is deposited on thin amorphous carbon films and subjected to a structure analysis by (scanning) TEM ((S)TEM). This method serves as a two-in-one synthesis and TEM sample-preparation technique and allows straightforward analysis of ZIF-8 crystallites. Artifacts resulting from sample preparation are completely avoided by this approach. The morphological properties, crystal structure, and the chemical composition of the material are investigated with high spatial resolution by a variety of methods of (analytical) electron microscopy. Furthermore, the incorporation of metallic nanoparticles in ZIF-8 by integrating a corresponding step into the layer-by-layer deposition process is examined. The formation of ZIF-8 crystals on the film proceeds as under the absence of nanoparticle-forming synthesis steps. However, the nanoparticles rather cover the supporting amorphous carbon film than being incorporated in the ZIF-8 material. This information cannot be obtained from standard characterization techniques but requires the application of analytical (S)TEM techniques.