Quantum size effects in adatom island decay

The decay of hexagonal Ag adatom islands on top of larger Ag adatom islands on a Ag(111) surface is followed by a fast-scanning tunneling microscope. Islands do not always show the expected increase in decay rate with decreasing island size. Rather, distinct quantum size effects are observed where the decay rate decreases significantly for islands with diameters of 6, 9.3, 12.6, and 15.6 nm. We show that electron confinement of the surface state electrons is responsible for this enhancement of the detachment barrier for adatoms from the island edge.     

Optimal conditions for submonolayer nanoisland growth in ion beam assisted deposition

We study the optimal conditions for nanoisland growth in ion beam assisted deposition (IBAD). This situation occurs when adatom islands remain small enough to prevent the onset of three-dimensional growth, while at the same time preventing ion-induced surface erosion. To this end, we develop a rate equation model of IBAD, which embodies continuous deposition of adatoms and creation of vacancies, recombination of vacancies at adatom island edges, as well as recombination of adatoms at vacancy island edges. These rate equations are solved by numerical simulations based on the particle coalescence method. To determine the optimal growth condition, we find the largest mean size of the vacancy islands leading to their survival. We show that at this onset between the rough and smooth layer-by-layer growth regimes there is a simple exponential relation between the largest size of the vacancy islands and the external control parameters of the growth.     

Nanowedge island formation on Mo(1 1 0)

The deposition of ultrathin Fe films on the Mo(1 1 0) surface at elevated temperatures results in the formation of distinctive nanowedge islands. The model of island formation presented in this work is based on both experiment and DFT calculations of Fe adatom hopping barriers. Also, a number of classical molecular dynamics simulations were carried out to illustrate fragments of the model. The islands are formed during a transition from a nanostripe morphology at around 2 ML coverage through a Bales-Zangwill type instability. Islands nucleate when the meandering step fronts are sufficiently roughened to produce a substantial overlap between adjacent steps. The islands propagate along the substrate [0 0 1] direction due to anisotropic diffusion/capture processes along the island edges. It was found that the substrate steps limit adatom diffusion and provide heterogeneous nucleation sites, resulting in a higher density of islands on a vicinal surface. As the islands can be several layers thick at their thinnest end, we propose that adatoms entering the islands undertake a so-called “vertical climb” along the sides of the island. This is facilitated by the presence of mismatch-induced dislocations that thread to the sides of the islands and produce local maxima of compressive strain. Dislocation lines also trigger initial nucleation on the surface with 2-3 ML Fe coverage. The sides of the nanowedge islands typically form along low-index crystallographic directions but can also form along dislocation lines or the substrate miscut direction.     

Quantum size effect on adatom surface diffusion

Using scanning tunneling microscopy, we demonstrate that the nucleation density of Fe islands on the surface of nanoscale Pb films oscillates with the film thickness, providing a direct manifestation of the quantum size effect on surface diffusion. The Fe adatom diffusion barriers were derived to be 204+/-5 and 187+/-5 meV on a 21 and 26 monolayer (ML) Pb film, respectively, by matching the kinetic Monte Carlo simulations to the experimental island densities. The effect is further illustrated by the growth of Fe islands on wedged Pb films, where the Fe island density is consistently higher on the odd-layer films than on the even-layer films in the thickness range of 11 to 15 ML.     

薄膜生长中的表面动力学(Ⅱ)

本文较全面地从理论上研究了薄膜生长过程中原子在表面上的各种动力学表现，涉及的内容包括亚单层生长时，原子在表面上的扩散，粘接，成核，以及已经形成的原子岛之间的相互作用，兼并，失稳，退化等一系列过程。在第一部分(即0—6章，刊登在《物理学进展》23卷1期上)介绍了薄膜生长动力学的基础之后，从第7章开始我们侧重研究一个在向同性和各向异性表面都普遍成立的原子岛尺寸大小及密度分布的标度定律；建立了一套研究在各向同性和各向异性表面上二维原子岛退化过程的广义动力学标度理论。基于对层间质量扩散通道的研究，本文提出了两种不同的原子下跃机制，既任意跃迁机制和选择跃迁机制，并做了进一步的实验验证。利用这一新的层间质量扩散机制，我们成功地解释了实验上观测到的三维原子岛的退化规律。更加有趣的是，本文讨论了应力对岛的形状和各种动力学规律的影响。在最后我们还提出了一个利用凝聚能转化来控制二维原子岛生长的方法，其目的是希望能够找到一种人为有效地在表面上制备低维量子结构的方法。     

薄膜生长中的表面动力学(Ⅱ)

本文较全面地从理论上研究了薄膜生长过程中原子在表面上的各种动力学表现 ,涉及的内容包括亚单层生长时 ,原子在表面上的扩散 ,粘接 ,成核 ,以及已经形成的原子岛之间的相互作用 ,兼并 ,失稳 ,退化等一系列过程。在第一部分 (即 0～ 6章 ,刊登在《物理学进展》2 3卷 1期上 )介绍了薄膜生长动力学的基础之后 ,从第 7章开始我们侧重研究一个在向同性和各向异性表面都普遍成立的原子岛尺寸大小及密度分布的标度定律 ;建立了一套研究在各向同性和各向异性表面上二维原子岛退化过程的广义动力学标度理论。基于对层间质量扩散通道的研究 ,本文提出了两种不同的原子下跃机制 ,既任意跃迁机制和选择跃迁机制 ,并做了进一步的实验验证。利用这一新的层间质量扩散机制 ,我们成功地解释了实验上观测到的三维原子岛的退化规律。更加有趣的是 ,本文讨论了应力对岛的形状和各种动力学规律的影响。在最后我们还提出了一个利用凝聚能转化来控制二维原子岛生长的方法 ,其目的是希望能够找到一种人为有效地在表面上制备低维量子结构的方法。     

Time evolution of adatom and vacancy clusters on Ag(110)

The time evolution of adatom and vacancy islands on an Ag(110) surface is studied by using a variable-temperature ultrahigh vacuum scanning tunneling microscope. The islands are created by Ar⁺ ion sputtering at low temperatures and at very low fluxes (0.004 ML s⁻¹). The area of both kinds of island decreases linearly as a function of time, at least for small islands. The experimental results are compared with kinetic Monte Carlo simulations.     

Long-range electronic interactions at a high temperature: bromine adatom islands on Cu(111)

Long-range electronic interactions between Br adatom islands, which are formed at approximately 600 K, on Cu(111) are mediated by substrate surface-state electrons at that elevated temperature. Using scanning tunneling microscopy at 4 K, we have quantified nearest neighbor island separations and found favored spacings to be half-multiples of the Fermi wavelength of Cu(111). The strong interaction potential and decay length of the interisland interactions are discussed in terms of the interaction of Br with the substrate surface state.     

Cu(111)三维表面岛对表面原子扩散影响的分子动力学研究

采用嵌入原子方法的原子间相互作用势，利用分子动力学方法计算了同质外延生长中不同层数的三维Cu(111)表面岛上表面原子扩散激活能，分析了三维表面岛的层数对表面原子交换扩散和跳跃扩散势垒的影响. 研究结果表明，二维Enrilich-Schwoebel(ES)势垒小于三维ES势垒，且三维ES势垒不随表面岛层数的增加而显著变化. 对于侧向表面为(100)的表面岛，表面原子沿〈011〉方向上的扩散行为，随表面岛层数增加而逐渐变化；在表面岛层数达到3层时，扩散路径上的势垒变化趋于稳定，表面原子扩散以下坡扩散为主. 对于侧面取向为(111)的表面岛，当表面岛层数大于3层后，开始呈现上坡扩散的可能. 关键词： 表面原子 扩散 分子动力学模拟     

Nonmean-Field Model for Ostwald Ripening of Two-Dimensional Islands

A nonmean-field model for the ripening of two-dimensional islands is presented. In this model, the adatom sea is divided into many small cells that are the polygons of a Voronoi network. The chemical potentials of adatom seas surrounding different islands are different. Strain generated by lattice mismatch is introduced into the model.Computer simulation under periodic boundary conditions is carried out to describe the island ripening in two cases (with and without strain), and demonstrates that small islands may grow faster than large islands, which cannot occur in the mean-field model. The simulated results also show that including strain will slow down the evolution of average island size, and an explanation for this is given.     

Stability and diffusion of surface clusters

Using kinetic Monte Carlo simulations and a bond-counting ansatz, thermal stability and diffusion of an adatom island on a crystal surface are studied. At low temperatures, the diffusion constant D is found to decrease for a wide range of island sizes like , where is close to one, N being the number of adatoms in the cluster. By heating up the surface, the system undergoes a phase transition above which the island disappears. Characteristics of that transition are discussed. Received 20 January 1999     

动力学晶格蒙特卡洛方法模拟Cu薄膜生长

利用动力学晶格蒙特卡洛方法模拟了Cu薄膜在Cu(100)面上的三维生长过程。模型中考虑了四个动力学过程:原子沉积、增原子迁移、双原子迁移和台阶边缘原子迁移,各动力学过程发生的概率由多体势函数确定。讨论了基底温度、沉积速率及原子覆盖率对Cu原子迁移、成核和表面岛生长等微观生长机制的影响;获得了Cu薄膜的表面形貌图并计算了表面粗糙度。模拟结果表明,随基底温度升高或沉积速率下降,岛的平均尺寸增大,数目减少,形状更加规则。低温时,Cu薄膜表现为分形的离散生长,高温时,Cu原子迁移能力增强形成密集的岛。Cu薄膜表面粗糙度随着基底温度的升高而迅速减小;当基底温度低于某一临界温度时,表面粗糙度随原子覆盖率或沉积速率的增大而增大;当基底温度超过临界温度时,表面粗糙度随原子覆盖率或沉积速率的变化很小,基本趋于稳定。     

Study of nanoclusters growth at initial stages of ultrathin film deposition by kinetic modeling

Comparative analysis of Au, Cu, Pt, Ni and Fe nanoclusters growth on amorphous carbon substrate by proposed kinetic model based on rate equations is present. Partial sticking coefficients introduced into the model let to discriminate elementary processes such as adatom adsorption and diffusion on bare substrate and on top of islands, nucleation and mobility of islands and its coalescence, 2-d and 3-d island growth modes. The quantitative fittings of experimental time dependencies of surface coverage, clusters density, cluster size are performed by solving model equations. From the best fittings the values of phenomenological coefficients defining elementary processes are found for different materials. Comparative analysis of those coefficients let to discover mechanisms of nanoclusters formation and growth of different materials. It is shown that clusterization for Cu and Au is more favorable than for Pt and Ni. Diffusivity for Pt and Ni on amorphous carbon (a-C) substrate is significantly less than for Au and Cu. In opposite, diffusivity on the top of islands for Ni and Pt is significantly higher than for Au and Cu. The mobility of islands for Au and Cu is much higher than for Ni and Pt. The fitting of experimental curves of Fe deposition on a-C at different temperatures showed that temperature mainly influences sticking process but not diffusion.     

Study of the island morphology at the early stages of Fe/Mo(110) MBE growth

We present theoretical study of morphology of Fe islands grown at Mo(110) surface in submonolayer MBE mode. We utilize atomistic SOS model with bond counting, and interactions of Fe adatom up to third nearest neighbors. We performed KMC simulations for different values of adatom interactions and varying temperatures. We have found that, while for the low temperature islands are fat fractals, for the temperature 500 K islands have faceted rhombic-like shape. For the higher temperature, islands acquire a rounded shape. In order to evaluate qualitatively morphological changes, we measured average aspect ratio of islands. We calculated dependence of the average aspect ratio on the temperature, and on the strength of interactions of an adatom with neighbors.      

Reversible shape transition of pb islands on Cu(111)

Using low-energy electron microscopy, we have observed a reversible transition in the shape of Pb adatom and vacancy islands on Cu(111). With increasing temperature, circular islands become elongated in one direction. In previous work we have shown that surface stress domain patterns are observed in this system with a characteristic feature size which decreases with increasing temperature. We show that the island shape transition occurs when the ratio of the island size to this characteristic feature size reaches a particular value. The observed critical ratio matches the value expected from stress domains.     

基底显微结构对薄膜生长影响的Monte Carlo模拟研究

利用Monte Carlo方法研究了基底显微结构对薄膜生长的影响. 对不同显微结构基底上薄膜生长的初始阶段岛的形貌和尺寸与薄膜覆盖度和入射粒子沉积速率之间的关系进行了模拟和分析. 模型中考虑了粒子沉积、吸附粒子扩散和蒸发等过程. 结果表明,基底显微结构对薄膜生长具有明显影响. 当沉积温度为300K、沉积速率为0.005ML/s（Monolayer/second,简称ML/s）、覆盖度为0.05ML时,四方基底上薄膜生长呈现凝聚生长. 随着覆盖度增加,岛的尺寸变大,岛的数目减少. 而对于六方基底,当覆盖度从0.05ML变化到0.25ML时,薄膜生长经历了一个从分散生长过渡到分形生长的过程. 无论是四方还是六方基底,随着沉积速率的增加,岛的形貌由少数聚集型岛核分布状态向众多各自独立的离散型岛核分布状态过渡.     

The effect of embedded Pb on Cu diffusion on Pb/Cu(1 1 1) surface alloys

We have used scanning tunneling microscopy and low-energy electron microscopy to measure the thermal decay of two-dimensional Cu, Pb-overlayer, and Pb-Cu alloy islands on Pb-Cu(1 1 1) surface alloys. Decay rates covering 6-7 orders of magnitude are accessible by applying the two techniques to the same system. We find that Cu adatom diffusion across the surface alloy is rate-limiting for the decay of both Pb and Pb-Cu islands on the surface alloy and that this rate decreases monotonically with increasing Pb concentration in the alloy. The decrease is attributed to repulsive interactions between Cu adatoms and embedded Pb atoms in the surface alloy. The measured temperature dependences of island decay rates are consistent with first-principles calculations of the Cu binding and diffusion energies related to this “site-blocking” effect.     

Size-dependent detachment-limited decay kinetics of two-dimensional TiN islands on TiN(111)

In situ high-temperature (T(a)=1050-1250 K) scanning tunneling microscopy was used to determine the coarsening and decay kinetics of two-dimensional TiN adatom and vacancy islands on atomically smooth TiN(111) terraces. We report the first observation of an abrupt decrease in decay rates, irrespective of T(a), of adatom islands with areas less than a critical value of 1600 A(2). However, no decay rate transition was observed for vacancy islands. We attribute the size-dependent island decay behavior, which is consistent with detachment-limited kinetics, to anisotropic attachment and detachment barriers.     

Kinetic Monte Carlo simulations of Pd deposition and island growth on MgO(1 0 0)

The deposition and ripening of Pd atoms on the MgO(1 0 0) surface are modeled using kinetic Monte Carlo simulations. The density of Pd islands is obtained by simulating the deposition of 0.1 ML in 3 min. Two sets of kinetic parameters are tested and compared with experiment over a 200-800 K temperature range. One model is based upon parameters obtained by fitting rate equations to experimental data and assuming the Pd monomer is the only diffusing species. The other is based upon transition rates obtained from density functional theory calculations which show that small Pd clusters are also mobile. In both models, oxygen vacancy defects on the MgO surface provide strong traps for Pd monomers and serve as nucleation sites for islands. Kinetic Monte Carlo simulations show that both models reproduce the experimentally observed island density versus temperature, despite large differences in the energetics and different diffusion mechanisms. The low temperature Pd island formation at defects is attributed to fast monomer diffusion to defects in the rate-equation-based model, whereas in the DFT-based model, small clusters form already on terraces and diffuse to defects. In the DFT-based model, the strong dimer and trimer binding energies at charged oxygen vacancy defects prevent island ripening below the experimentally observed onset temperature of 600 K.     

Electron and atom dynamics at solid surfaces and relation to epitaxy

At the surface, the three dimensional symmetry of a solid is broken. Electrons and atoms near the surface may rearrange to lower the free energy of the system. Scattering by defects and confinement by boundaries of electrons may produce long-range charge density oscillations. Adatoms interact with each other via mutual perturbation of the surface, known as indirect electronic and elastic interactions. These interactions are very weak and are also oscillatory. For some systems, formation of adsorption layer superstructures can be directly correlated to adatom–adatom interactions. When the temperature is raised, adatoms and admolecules can start to diffuse, interact, or react. They may aggregate into clusters and islands, and grown into a thin film. The stability of clusters may exhibit magic numbers in size and thickness. When the temperature is changed, island shape transitions may occur. The growth of islands and ultra-thin films can also be influenced by electronic effects as well as by the addition of a surfactant layer. All these growth behaviors in epitaxy can be understood from the mechanisms and energetics of elementary surface atomic processes, and atom and electron dynamics. They, in turn, can be studied in details using atomic resolution microscopy.