Two-scale modeling of adsorption processes at structured surfaces

We present an algorithm for the simulation of vicinal surface growth. It combines a lattice gas anisotropic Ising model with a phase-field model. The molecular behavior of individual adatoms is described by the lattice gas model. The microstructure dynamics on the vicinal surface are calculated using the phase-field method. In this way, adsorption processes on two different length scales can be described: nucleation processes on the terraces (lattice gas model) and step-flow growth (phase field model). The hybrid algorithm that is proposed here, is therefore able to describe an epitaxial layer-by-layer growth controlled by temperature and by deposition rate. This method is faster than kinetic Monte Carlo simulations and can take into account the stochastic processes in a comparable way.     

Corroboration of a multiscale approach with all atom calculations in analysis of dislocation nucleation from surface steps

We present a comparative study of the influence of atomic-scale surface steps on dislocation nucleation at crystal surfaces based on an all atom method and a hierarchal multiscale approach. The multiscale approach is based on the variational boundary integral formulation of the Peiersl–Nabarro dislocation model in which interatomic layer potentials derived from atomic calculations of generalized stacking fault energy surfaces are incorporated. We have studied nucleation of screw dislocations in two bcc material systems, molybdenum and tantalum, subjected to simple shear stress. Compared to dislocation nucleation from perfectly flat surfaces, the presence of atomic scale surface steps rapidly reduces the critical stress for dislocation nucleation by almost an order of magnitude as the step height increases. In addition, they may influence the slip planes on which dislocation nucleation occurs. The results of the all atom method and the multiscale approach are in good agreement, even for steps with height of only a single atomic layer. Such corroboration supports the further use of the multiscale approach to study dislocation nucleation phenomena in more realistic geometries of technological importance, which are beyond the reach of all current atom simulations.     

A phase-field/Monte-Carlo model describing organic crystal growth from solution

In this paper work we present a phase-field/Monte-Carlo hybrid algorithm for the simulation of solutal growth of organic crystals. The algorithm is subsequently used for an investigation of diffusion effects on the growth mechanisms. This method combines a two-scale phase-field model of the liquid phase epitaxial growth and a Monte-Carlo algorithm of the 2D nucleation and thus is faster than previous purely Monte Carlo simulations of crystal growth. The inclusion of supersaturation and diffusion in the method allows the study of crystal growth under various growth conditions. Parameters used in the hybrid algorithm are bound to the energetic parameters of crystal faces, which can be estimated from a detailed study of the actual crystal structure based on a connected nets analysis, which allows the prediction of the shape and morphology of real crystals. The study of the diffusion effect is carried out based on an example of a hydroquinone crystal, which grows from the water solution at various supersaturations. The dependencies of the growth rate and the nucleation rate on the supersaturation indicate the change of the growth mechanism from spiral growth to 2D nucleation. The difference in the growth rate for various faces is in agreement with the crystal morphologies derived from the attachment energy method and observed experimentally. The main result of the simulation is the evaluation of engineering limits for choosing appropriate external process conditions.     

微液滴在不同能量表面上润湿状态的分子动力学模拟

微小液滴在不同能量表面上的润湿状态对于准确预测非均相核化速率和揭示界面效应影响液滴增长微观机理具有重要意义. 通过分子动力学模拟, 研究了纳米级液滴在不同能量表面上的铺展过程和润湿形态. 结果表明, 固液界面自由能随固液作用强度增加而增加, 并呈现不同液滴铺展速率和润湿特性. 固液作用强度小于1.6的低能表面呈现疏水特征, 继续增强固液作用强度时表面变为亲水, 而固液作用强度大于3.5的高能表面上液体呈完全润湿特征. 受微尺度条件下非连续、非对称作用力影响, 微液滴气液界面存在明显波动, 呈现与宏观液滴不同的界面特征. 统计意义下, 微小液滴在不同能量表面上铺展后仍可以形成特定接触角, 该接触角随固液作用强度增加而线性减小, 模拟结果与经典润湿理论计算获得的结果呈现相似变化趋势. 模拟结果从分子尺度为核化理论中的毛细假设提供了理论支持, 揭示了液滴气液界面和接触角的波动现象, 为核化速率理论预测结果和实验测定结果之间的差异提供了定性解释.     

Order parameter modeling of fluid dynamics in narrow confinements subjected to hydrophobic interactions

A novel phase-field approach is developed for quantitative modeling of the complex thermophysics over reduced length scales in narrow fluidic confinements, as induced by the surface roughness-hydrophobicity coupling and the consequent hydrodynamic interactions. The method is tested for flows on micro- and nano- corrugated surfaces in narrow confinements, and the agreement with molecular dynamics and lattice Boltzmann simulations is found to be quantitative.     

Uncommon dislocation processes at the incipient plasticity of stepped gold surfaces

Gold vicinal surfaces (788), with a high density of steps, along with (111) flat surfaces taken as a reference, have been nanoindented and their resulting penetration curves and related defect structure comparatively analyzed by AFM and atomistic simulations. Stepped surfaces are shown to yield at smaller loads than (111) ones in agreement with calculations of the critical resolved shear stress needed to nucleate a dislocation. In the stepped surfaces, a novel intermediate state is identified in which the penetration curves depart from a Hertzian behavior prior to the appearance of pop-ins. This state is shown to result from heterogeneous nucleation at preexisting surface steps of dislocation loops, most of which retract and vanish when the indenter load is removed.     

Nucleation barriers for the liquid-to-crystal transition in simple metals: Experiment vs. simulation

Crystal nucleation in the one-component metals Ni and Au is investigated using a combination of differential thermal analysis (DTA) experiments and Monte Carlo (MC) simulations. A novel experimental methodology allows to measure nucleation rates J over a range of 8 orders of magnitude. Evidence is given that these rates correspond to homogeneous nucleation. From the nucleation rates, free energy nucleation barriers ΔG ^? are extracted using an ansatz obtained in the framework of classical nucleation theory (CNT). The latter ansatz is rationalized by MC simulations that directly yield estimates for the temperature dependence of ΔG ^?. The values of ΔG ^?, as determined from the simulation, are in very good agreement with those extracted from the experiments. The simulations indicate that in the range where experiments are available the corrections to CNT are relatively small, thus justifying the application of CNT. We also discuss how the conditions for heterogeneous nucleation on a flat or structured wall can be obtained from computer simulations.     

Unified phase-field model for epitaxial growth of multi-scale three-dimensional islands on insulating surfaces

In this paper we present a unified phase-field model for non-equilibrium growths of various three-dimensional metal islands on insulating surfaces. We introduce a phase-field variable to distinguish the island from the non-island regions and substrate and a density variable to describe local density of deposited adatoms. Two partial differential equations with appropriate boundary conditions, as the governing equations, are used to describe the evolution of the three-dimensional metal islands and the diffusion of adatoms. We solve the equations by using an adaptive mesh refinement method so that we can simulate the non-equilibrium growth of three-dimensional metal islands from tens of nanometers to several micrometers. We investigate the dependence of simulated results on the model parameters and experimental conditions. Equilibrium shape of such islands can be obtained through sufficient post-deposition relaxation. Experimental trends of island size and shape on various scales are obtained with reasonable parameters. This method should be a good approach to non-equilibrium growths of multi-scale three-dimensional metal islands.     

Direct visualisation of homogeneous and heterogeneous crystallisation in an ensemble of confined domains of poly(ethylene oxide)

We present a study of homogeneous and heterogeneous nucleation in polymer crystallisation. In bulk samples the crystallization is typically dominated by nucleation from defects (heterogeneous nucleation), and consequently studies must rely on sample preparation to minimize this effect. We present a study of nucleation within discrete droplets of poly(ethylene oxide) that are formed by the dewetting of a thin film on an unfavourable substrate. The samples provide an ensemble of impurity-free droplets, with length scales that can easily be measured. We show that the data for heterogeneous and homogeneous nucleation is qualitatively different, and that the data mirrors the fundamental differences in the underlying mechanisms for the two nucleation processes. The experiments presented here provide a simple method that can be used to study heterogeneous and homogeneous nucleation in great detail.Received: 1 January 2003, Published online: 30 October 2003PACS: 61.41. + e Polymers, elastomers, and plastics - 68.55.-a Thin film structure and morphology - 81.10.-h Methods of crystal growth; physics of crystal growth     

Scale-bridging phase-field simulations of microstructure responses on nucleation in metals and colloids

In the present studies we investigate the connection between atomistic simulation methods, i.e. molecular dynamics (MD) and phase-field crystal (PFC), to the mesoscopic phase-field methods (PFM). While the first describes the evolution of a system on the basis of motion equations of particles the second uses a Cahn–Hilliard type equation to described an atomic density field and the third grounds on the evolution of continuous local order parameter field. The first aim is to point out the ability of the mesoscopic phase-field method to make predictions of growth velocity at the nanoscopic length scale. Therefore the isothermal growth of a spherical crystalline cluster embedded in a melt is considered. We also show simulation techniques that enable to computationally bridge from the atomistic up to the mesoscopic scale. We use a PFM to simulate symmetric thermal dendrites started at an early stage of solidification related to nucleation. These techniques allow to simulate three dimensional dendrites from the state of nuclei (≈50?Å) converted from MD up to a size of some μm where ternary side-arms start to grow.     

不同衬底条件下石墨烯结构形核过程的晶体相场法研究

利用可描述气-固转变的三模晶体相场模型,在原子尺度上研究了不同衬底条件下石墨烯结构的形核过程.结果表明:无论衬底存在与否,气态原子均是先聚集为无定形过渡态团簇,随着气态原子的不断堆积和固相团簇中原子位置的不断调整,过渡态团簇逐渐转变为有序的石墨烯晶核,在此过程中,五元环结构具有重要的过渡作用;石墨烯在结构匹配较好的衬底(如面心立方(face-centered cubic,FCC)结构(111)和(110))上生长时,可形成几乎没有结构缺陷单晶石墨烯岛;在无衬底或结构匹配性较差的衬底(如FCC结构(100)面)上生长时,形成的石墨烯岛结构缺陷和晶界较多,不利于高质量石墨烯的制备.     

Patterned nucleation control in vacuum deposition of organic molecules

We report a generally applicable method to pattern organic molecules on mesoscopic scales. In our method, organic molecular beam deposition was conducted on substrate surfaces prepatterned with materials to which the organic molecules have larger binding energies in comparison to the substrate. Fully uniform nucleation control at these predefined locations can be achieved by an appropriate selection of the growth parameters including temperature and deposition rate. The physical mechanisms involved are studied by Monte Carlo simulations and stand in good agreement with the experimental findings.     

Elastic and plastic effects on heterogeneous nucleation and nanowire formation

We investigate theoretically the effects of elastic and plastic deformations on heterogeneous nucleation and nanowire formation. In the first case, the influence of the confinement of the critical nucleus between two parallel misfitting substrates is investigated using scaling arguments. We present phase diagrams giving the nature of the nucleation regime as a function of the driving force and the degree of confinement. We complement this analytical study by amplitude equations simulations. In the second case, the influence of a screw dislocation inside a nanowire on the development of the morphological surface instability of the wire, related to the Rayleigh-Plateau instability, is examined. Here the screw dislocation provokes a torsion of the wire known as Eshelby twist. Numerical calculations using the finite element method and the amplitude equations are performed to support analytical investigations. It is shown that the screw dislocation promotes the Rayleigh-Plateau instability.     

Molecular dynamics simulations of the formation for NaCl cluster at the interface between the supersaturated solution and the substrate

Molecular dynamics simulations of supersaturated aqueous NaCl solution including the Pt(100) or NaCl(100) crystal surfaces have been performed at an average temperature of 298 K. The behavior of the NaCl cluster produced in the solution have been studied through the consideration of the water dielectric property near the crystalline surfaces for understanding the role of crystal growth on the surface. The surfaces in the solutions greatly influence heterogeneous nucleation in crystallization process. Density profile of the supersaturated solution and polarization of water molecules was calculated in order to describe the effect of the surfaces on the solution structure at the solid–liquid interfaces. The formation levels of NaCl clusters heavily depended on the water orientation at the interfaces. NaCl clusters were easily formed near the Pt(100) surface compared with the NaCl(100) surface owing to a different construction of water molecules between the platinum and NaCl surface.     

Melting, freezing and nucleation in nanoclusters of potassium chloride

Molecular dynamics simulations of the melting, freezing and nucleation are presented for unconstrained nanoclusters of KCl with a number of ions between 512 and 10648. The maximum extent of the probed liquid supercooling is analysed to the light of theoretical predictions and compared with experimental data. The fraction of the solid-like ions in the supercooled liquid is used as an indicator of heterogeneities within the liquid. Induced nucleation by seeding the supercooled liquid indicates that solid-liquid coexistence is stable, and sustained during the lifetime of the clusters, relatively to the supercooled liquid. A phenomenological analysis on the relaxation times of the crystal growth process is made. Critical nuclei sizes computed from the effectiveness of the seeds in the heterogeneous nucleation of the supercooled liquid, and from the residual crystallites in clusters not totally melted, are presented as a function of the temperature. The behavior of the systems is followed through various properties such as liquid and solid molar fractions, enthalpies of melting, heat capacities, self-diffusion coefficients and relaxation times related to the freezing process. The consistency of the simulation results for the heterogeneous nucleation is assessed by means of a classical nucleation model, from which an estimate of the interfacial surface tension is also worked out and compared with experimental data.     

稀土元素La对Ni75B17Si8非晶合金形成能力和热稳定性的影响

本文发现微量稀土元素在某些合金中可不呈均匀固溶态分布,而与母合金某些原子反应生成高熔点化合物,或吸附于合金中异质核心表面改变其异质形核的活性。当稀土元素以这种状态存在时,不但失去稳定非晶相的作用,而且促进异质形核,降低合金的非晶形成能力和热稳定性。 关键词：     

力和扩散机理下外延形貌的演化分析

本文提出了一个新的基于扩散界面的相场模型来描述外延生长中岛的形核、生长及熟化过程. 该模型同时考虑了弹性场、表面能、沉积、扩散、解吸和能量势垒等热力学及动力学过程对表面纳米形貌的影响. 采用经典的BCF模型来描述生长中的扩散形核过程, 而采用一个新的包含弹性应变能的自由能函数, 通过变分得到一个描述多层岛生长的相场方程, 该方法可以有效地描述外延生长中复杂的外延形貌. 采用有限差分格式对非线性耦合方程组进行求解. 数值结果显示, 该模型可以真实地再现外延生长中多层岛结构(即山丘状形貌)的演化过程, 模拟结果与已有实验结果一致. 同时模拟了生长过程中随外延形貌演化而形成的复杂生长应力, 研究表明, 在生长过程中, 岛中存在着复杂的应力分布, 且在岛边界处应力达到局部最大, 这与实验结果定性一致. 此外, 本文的重要发现是, 外延生长中的应力演化明显地影响原子的扩散过程, 当应力存在时, 外延结构变化较无弹性场时变快. 该项研究对理解外延生长中各物理机理的协同作用有重要的指导意义.     

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.     

Domain wall nucleation and propagation in spin-transfer torque switching with thermal effects

We conduct micro-magnetic simulations to study spin-transfer torque induced magnetization switching in perpendicular magnetic tunneling junctions. The effects of current densities and temperatures on the switching processes are studied in details. We then proposed an approach to compute the deterministic switching time by taking thermal-effect into account. The switching time is less temperature-dependent under higher current density; however, as the current density decreases, the effect of temperature on the switching time becomes more and more significant. The switching process with micro-magnetic simulations is shown to be via domain wall nucleation and propagation. The phenomena are consistent with the recent experimental found-out. We further propose a method to compute the switching time based on domain wall nucleation and propagation theory, and compare the switching time with those from macro-spin approximation. It is found the switching times from the micro-magnetic simulations are much shorter than that from the macro-spin approximations. Macro-spin approximation over-estimates the switching times due to its coherent rotation assumptions.     

半导体硅重构表面及其相变动力学的研究进展

简单介绍了文章作者在半导体硅重构表面及其相变动力学研究方面的进展.近期Si(111) (7×7)-(1×1)相变的实验研究发现,将温度升高到相变温度以上时,7×7岛面积以恒定的衰减速率随时间减小至零,且初始面积越大的岛这个衰减速率就越大.文章作者分析了大量的实验事实,由此提出了一个双速相场模型来解释这个重要而令人困惑的现象.模型重点是：在相变过程中,7×7关键结构变化较快,随后的层错消解过程要慢得多.这个模型完美地解释了相关实验现象,说明该模型抓住了关键物理要素,这种相场方法也可以用于其他半导体表面相变研究.