Comparison of electronic structures of mass-selected Ag clusters and thermally grown Ag islands on sputter-damaged graphite surfaces

Ag cluster anions consisting of 3–16 atoms were deposited on sputter-damaged HOPG surfaces using a soft-landing technique (mean deposition energy less than 0.2 eV/atom) at room temperature. For investigations of the structures of deposited clusters, X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) were used. In addition, the chemical properties of deposited clusters were studied using atomic oxygen and CO. Comparison of the properties of deposited Ag clusters and Ag islands with similar sizes grown by evaporating Ag atoms on the same substrate shows different results, implying that two different preparation methods give either different shapes of Ag clusters and islands, or dissimilar metal–support interactions. PACS 73.22.-f     

Ag(111)和Au(111)上铋的初始生长行为

半金属铋(Bi)的表面合金具有的Rashba效应,和其具体结构性质有重要关联.本文结合扫描隧道显微镜(STM)和密度泛函理论(DFT),系统地研究了Bi原子在Ag(111)和Au(111)上的不同初始生长行为.在室温Ag(111)上,连续的Ag2Bi合金薄膜会优先在Ag台阶边缘形成;在570 K Ag(111)上,随着...     

Preferential heights in the growth of Ag islands on Si(1 1 1)-(7 × 7) surfaces

Growth behavior of thin Ag films on Si substrates at room temperature has been investigated by scanning tunneling microscopy and reflection high energy electron diffraction. In the layer-plus-island growth Ag islands show strongly preferred atomic scale heights and flat top. At low coverage (1 ML), islands containing two atomic layers of Ag are overwhelmingly formed. At higher coverages island height distribution shows strong peaks at relative heights corresponding to an even number (2, 4, 6, …) of Ag atomic layers. Beyond some coverage the height preference vanishes due to the appearance of screw dislocations and spiral growth.     

薄膜外延生长的计算机模拟

以Cu膜为例，用Monte-Carlo算法模拟了薄膜生长的随机过程，并提出了更加完善的模型.在合理选择原子间相互作用计算方法的基础上，考虑了原子的吸附、在生长表面的迁移及迁移所引起的近邻原子连带效应、从生长表面的脱附等过程.模拟计算了薄膜的早期成核情况以及表面粗糙度和相对密度.结果表明，随着衬底温度的升高或入射率的降低，沉积在衬底上的原子逐步由离散型分布向聚集状态过渡形成一些岛核，并且逐步由二维岛核向三维岛核过渡.在一定的原子入射率下，存在三个优化温度，成核率最高时的最大成核温度Tn、薄膜的表面粗糙度最低 关键词： Monte-Carlo算法 计算机模拟 薄膜生长     

Admetal-induced substrate surface restructuring during metal-on-metal electrochemical deposition studied by in situ scanning tunneling microscopy

Based on time-dependent in situ scanning tunneling microscopy (STM) studies, we demonstrate that for Ni on Ag(111) and Ru on Au(111), electrochemical metal-on-metal deposition can result in pronounced substrate surface restructuring. For Ni/Ag(111), we observe that at low deposition flux and low coverage, Ni submonolayer islands at steps are partly embedded in the Ag terraces, whereas at higher deposition flux and higher coverage, substrate restructuring results in the formation of monolayer bays in the Ag terraces. We suggest that this restructuring process proceeds predominantly via step edge diffusion of Ag atoms. For Ru/Au(111), the formation of fjords and monolayer holes in the Au terraces is observed at low and high Ru coverage, respectively. The importance of the Au surface mobility for the restructuring process is demonstrated by comparing experiments in H₂SO₄ and HCl solutions, in which Au exhibits strongly different surface mobilities. For this system, restructuring involves Au diffusion along Au steps, Au atom detachment from the Au steps, and upward exchange diffusion. According to these observations and their comparison with similar findings for vacuum deposition, we conclude that this restructuring requires (i) a high substrate surface mobility and (ii) a stronger bonding of substrate atoms to deposit islands than to the substrate.     

EM, XPS and LEED study of deposition of Ag on hydrogenated Si substrate prepared by wet chemical treatments

The deposition of Ag on a hydrogenated Si(111) substrate, prepared by wet chemical treatment, was carried out at room temperature (RT), 250°C and above 350°C. The samples were examined in situ by LEED, XPS and then by SEM and TEM. Our results show that flat Ag crystallite domains are growing on the H/Si(111) surface at all three substrate temperatures. The h/w ratio of the islands increases but the density decreases with increasing substrate temperature which is attributed to the differences between hydrogenated and clean Si(111) surface. The so-called A-type and B-type domains resulting from analyses of TOF ICISS are attributed to twinning in the deposited layer.     

Au/Cu(001)异质外延岛演化的分子动力学研究

利用分子动力学弛豫方法模拟了Au/Cu(001)异质外延生长初期Au异质外延岛的形貌演化，分析了Au外延岛演化过程中的局域应力及与基体结合能随表面岛尺寸的变化. 研究结果表明：当异质外延岛小于7×7时，外延岛原子分布呈现赝Cu点阵形貌；当外延岛达到8×8后，外延岛内开始出现失配位错，失配位错数量随外延岛尺寸的增加而增加. 局域压力分析指出，外延岛上原子之间的近邻环境不同导致了所受应力的差异，而外延岛的形变则是由外延岛原子的应力分布所决定. 研究还发现，失配位错的产生导致错位原子与基体原子之间的结合强度减弱，但相对增加了非错位原子与基体原子之间的结合强度. 关键词： 异质外延 表面形貌 局域压力 分子动力学模拟     

金属薄膜在云母与富勒烯衬底上的电阻弛豫现象

超高真空环境中，在云母和富勒烯衬底上蒸镀半连续的Nb和Ag膜，同时对其进行了原位电阻测量．在人为地突然中断蒸镀之后的10min内，仔细研究了样品电阻随时间的自动缓变过程（弛豫）．实验发现，Nb/云母和Ag/C₆₀样品的电阻随时间缓慢增加，Ag/云母样品的电阻随时间逐渐减小．样品弛豫的强度与衬底温度和金属膜厚度密切相关．分析表明，衬底上的金属原子徙动会引起金属岛的边际形变以及岛间融合，这是薄膜电阻弛豫的主要原因．电阻弛豫的方向与强度反映了金属膜/衬底系统的界面活性．衬底表面的缺陷也会影响这一弛豫过程．从微观的原子运动和宏观的热力学平衡这两方面描述了弛豫过程 关键词：     

Initial growth process and surface structure of Ag on Si(111) studied by low-energy Ion-Scattering Spectroscopy (ISS) and LEED-AES

The growth process of silver on a Si(111) substrate has been studied in detail by low-energy ion-scattering spectroscopy (ISS) combined with LEED-AES. Neon ions of 500 eV were used as probe ions of ISS. The ISS experiments have revealed that the growth at room temperature and at high temperature are quite different from each other even in the submonolayer coverage range. The following growth models have been proposed for the respective temperatures. At room temperature, the deposited Ag forms a two-dimensional (2D) island at around 2/3 monolayer (ML) coverage, where the Ag atoms are packed commensurately with the Si(111)1 substrate. One third of the substrate Si surface remains uncovered there. Then it starts to develop into Ag crystal, and at a few ML coverage a 3D island of bulk Ag crystal grows directly on the substrate. An intermediate layer, which covers uniformly the whole surface before the growth of Ag crystal, does not exist. At high temperatures (>~200°C), the well-known Si(111)√3-Ag layer is formed as an intermediate layer, which consists of 2/3 ML of Ag atoms and covers the whole surface uniformly. These Ag atoms are embedded in the first double layer of the Si substrate. It is concluded that the formation of the √3 structure needs relatively high activation energy which may originate from the large displacement of Si atoms owing to the embedment of the Ag atoms, and does not proceed below about 200°C. The most stable state of the Ag atoms on the outermost Si layer is in the shape of an island, both for the Si(111) surface and for the Si(111)√3-Ag surface.     

Ag growth on Si(111) with an Sb surfactant investigated by scanning tunneling microscopy

We have investigated a room-temperature growth mode of ultrathin Ag films on a Si(111) surface with an Sb surfactant using STM in a UHV system. On the Sb-passivated Si surface, small sized islands were formed up to 1.1 ML. Flat Ag islands were dominant at 2.1 ML, coalescing into larger islands at 3.2 ML. Although the initial growth mode of Ag films on the Sb-terminated Si(111) surface was Volmer-Weber (island growth), the films were much more uniform than Ag growth on clean (Si(111) at the higher coverages. From the analysis of STM images of Ag films grown with and without an Sb surfactant, the uniform growth of Ag films using an Sb surfactant appears to be caused by the kinetic effects of Ag on the preadsorbed Sb layer. Our STM results indicated that Sb suppresses the surface diffusion of Ag atoms and increases the Ag-island density. The increased island density is believed to cause coalescence of Ag islands at higher coverages of Ag, resulting in the growth of atomically flat and uniform Ag islands on the Sb surfactant layer.     

Coulomb attraction during the carpet growth mode of NaCl

The submonolayer growth of NaCl bilayer high-rectangular shaped islands on Ag(111) is investigated at around room temperature by using low temperature scanning tunneling microscopy. The growth at the step edges is preferred. Two kinds of islands are observed. They either grow with their non-polar edge at the step edge of Ag(111) or the islands overgrow in a carpet-like mode with the polar direction parallel to the edge. In the latter case, the Ag step is rearranged and considerable, while the NaCl layer is bent. This study clarifies the nature of the interaction of an alkali halide nanostructure with a metal step edge.     

锰的硅化物薄膜在Si(100)-2×1表面生长的STM研究

锰的硅化物在微电子器件、自旋电子学器件等领域具有良好的应用前景, 了解锰的硅化物薄膜在硅表面的生长规律是其走向实际应用的关键步骤之一. 本文采用分子束外延方法在Si(100)-2× 1表面沉积了约4个原子层的锰薄膜, 并利用超高真空扫描隧道显微镜研究了该薄膜与硅衬底之间在250-750℃范围内的固相反应情况. 室温下沉积在硅衬底表面的锰原子与衬底不发生反应, 薄膜由无序的锰团簇构成; 当退火温度高于290℃时, 锰原子与衬底开始发生反应, 生成外形不规则的枝晶状锰硅化物和富锰的三维小岛; 325℃时, 衬底上开始形成平板状的MnSi小岛; 525℃时, 枝晶状锰硅化物完全消失, 出现平板状的MnSi_1.7大岛; 高于600℃时, 富锰的三维小岛和平板状的MnSi小岛全部消失, 仅剩下平板状的MnSi_1.7大岛. 这些结果说明退火温度决定了薄膜的形态和结构. 在大约600℃退火时岛的尺寸随着退火时间的延长而逐渐增大, 表明岛的生长遵从扩散限制的Ostwald熟化机理.     

Interaction of Ag and O on W(1 1 0) studied by scanning tunneling microscopy

The structural changes of Ag films on W(1 1 0) upon coadsorption of oxygen have been studied by scanning tunneling microscopy. The exposure of one monolayer Ag to oxygen leads to a phase separation into an Ag bilayer and patches of O-covered W(1 1 0). The effective Ag island thickness increases linearly with oxygen exposure. For Ag submonolayer-islands the onset of the bilayer formation is delayed, the induction period increases with the available free W area. We conclude that the steps of the transport process are (1) dissociation of oxygen on W and on the Ag islands, (2) site exchange of atomic oxygen with Ag atoms predominantly at the island edges - while on W(1 1 0) the oxygen is immobile, (3) diffusion of the displaced Ag atoms to the island edges where they are incorporated into the monolayer and (4) initiation of Ag bilayer formation, once the W(1 1 0) is saturated with O. This indicates an unexpected activity of the Ag monolayer on W(1 1 0) towards oxygen dissociation. In case of a reversed deposition sequence, where submonolayer quantities of Ag are adsorbed on an oxygen-precovered W(1 1 0) surface, growth of Ag clusters is observed. The distribution of cluster size and cluster height depends critically on the spatial order within the predeposited oxygen overlayer - it is obvious that the oxygen overlayer on the W surface acts as a structured template for preferential Ag nucleation.     

Morphology and microstructure of Ag islands of aggregated atoms on oil surfaces

The morphology evolution of silver islands on silicone oil surfaces is measured and the microstructure of the islands is studied. The deposited Ag atoms diffuse and aggregate on the oil surface and then Ag islands with the width of the order of 102-nm form. After the samples are removed from the vacuum chamber, the immediate measurement shows that the apparent Ag coverage of the total area decays with the magnitude up to (23.0±3.8)% in few minutes. In the following two hours, the samples are kept in the ambient atmosphere and several unexpected results are detected: 1) as the topological structure of the islands evolves, the total area of each island decreases gradually and the maximum decrement measured is around 20%; 2) if an island breaks and becomes two small pieces, the total area decreases obviously; 3) however, if two small islands meet and stick together, a sudden increment of the total area is observed. These phenomena, mirroring the evolution process of the island microstructure, are resulted from both the diffusion of the atoms and the combination of the defects inside the islands.     

Single atomic manipulation and writing with scanning tunnelling microscopy at low temperatures

In the work reported in this paper,we have used a low-temperature scanning tunnelling microscope (LT-STM) system to manipulate accurately single atoms.We show how we can use a LT-STM to image and modify a bulk Ag(111) surface and manipulate Ag atoms from substrate and evaporated adsorbates on Ag(111) substrates.We present a synergistic combination of SM-induced modification and ordered arrays of nanometre-scale structures.In particular,we demonstrate the ability to modify Ag atomic nanometre structures on the Ag(111) substrate,and some English letters and a Chinese character can be written by single Ag atoms coming from the substrate and evaporated adsorbates on Ag(111),In this way ,we supply an effective basis to explore the fundamental physical properties of a nanometre structure and to develop nanotechnology with a bottom-up approach,     

Simulation of surfactant effects on the growth of metal homoexpitaxial Sb-Ag/Ag(111)

A kinetic Monte Carlo simulation is performed in order to study the effect of Sb atoms as a surfactant on the growth of Ag on Ag(111).In our model the repulsive mechanism in which the surfactant Sb atoms repel diffusing Ag adatoms,and the exchange mechanism between Ag and Sb atoms,are considered.Our simulations show that the effects of Sb atoms for Ag/Ag(111) growth system are mainly to increase the chances for Ag atoms to overcome the Ehrlich-Schwoebel barrier both in the interlayer growth and along the edge diffusion.The influence of the coverage of Sb atoms and substrate temperature on the growth of Ag/Sb/Ag(111) is discussed.     

Simulation of surfactant effect on growth of metal homoexpitaxial Sb－Ag/Ag(111)

A kinetic Monte Carlo simulation is performed in order to study the effect of Sb atoms as a surfactant on the growth of Ag on Ag(111). In our model the repulsive mechanism in which the surfactant Sb atoms repel diffusing Ag adatoms, and the exchange mechanism between Ag and Sb atoms, are considered. Our simulations show that the effects of Sb atoms for Ag/Ag(111) growth system are mainly to increase the chances for Ag atoms to overcome the Ehrlich--Schwoebel barrier both in the interlayer growth and along the edge diffusion. The influence of the coverage of Sb atoms and substrate temperature on the growth of Ag/Sb/Ag(111) is discussed.     

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.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

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。