包含少於1000 個原子的金屬納米顆粒會與此金屬的常規尺寸材料有很大差別。它們擁有一些特殊的物理和化學的性質，因而在過去的二十年中吸引了大量的研究工作。但是由於尺寸太小，對於這些納米結構的深入和全面的研究十分困難。掃描隧道顯微鏡方法是一種強大的研究此類問題的技術。它擁有的極強的空間分辨力和原子操縱的能力使得我們可以獲得一些納米顆粒的細緻信息。在這篇論文中，我將報道我的關於在半導體Si(111)-(7x7)的重構表面的貴金屬（銀/金）顆粒的研究。 / 我首先研究了在Si(111)-(7x7)上的金屬顆粒的製備方法。使用熱蒸發方法，我製備了在Si(111)-(7x7)上的金屬顆粒。在研究了這些金屬顆粒在半元胞中的的整體生長過程之後，我的研究集中在本論文的主要目標--獨立的銀納米顆粒上。通過仔細觀察記錄單個銀原子的擴散過程，我們確認了Ag3‐Ag13 顆粒中的原子數目。這些掃描隧道顯微鏡的圖像同時也指出了這些顆粒的動態性質，包括自發跳動、分解和與鄰近的單個Ag 原子的合成。為了獲得對這些Ag 顆粒的控制，我們找到了一種垂直操縱單個Ag 原子的方法。在樣品的表面，掃描隧道顯微鏡的針尖通過特定的程序被用來抓起和放下單個Ag 原子。它被用來組裝和拆裝Ag的顆粒。各種Ag 顆粒在半元胞中被組裝，同時我們發現單個半元胞中的最大的顆粒是Ag25。同時這項技術被用來組裝複雜的Ag 顆粒的圖形。 / 使用上面這些操縱的技術（熱蒸發方法和原子操縱方法），我們細緻的研究了顆粒的兩方面性質：第一，我們發現對於單個元胞中的Ag 顆粒都存在着顯著的電學的整流效應，同時我們比較了它們各自的特點。通過實驗測量和第一性原理計算，我們發現這種電學整流效應源自電子態密度的耦合效應。當這些顆粒在平面內連接起來從而增加橫向的尺寸時，這種顆粒的整流效應將會繼續存在；但當顆粒形成多層Ag 的結構即垂直方向尺寸增加時，這個整流效應將會消失。另外一個所研究的性質是所有的Ag顆粒都存在一種對周圍單個Ag原子的吸引作用，從而讓自身長大的過程。這一過程對於Ag 顆粒的生長起到了至關重要的作用。我們選擇了幾個有代表性的顆粒，通過原子操縱的方法測量了它們與一個鄰近的Ag 原子的融合過程。測量的結果說明一個顆粒的存在通常會降低一個鄰近Ag 原子向此顆粒擴散的勢壘高度，同時也會影響此單個原子在靠近此顆粒的吸附位上的吸附能。 / Metal nanoclusters with less than 1000 atoms differ very much from their bulk counterparts. They possess many unique chemical and physical properties and have attracted extensive studies during the past two decades. However, in-depth and comprehensive researches of these structures are difficult for their small size. Scanning tunneling microscopy (STM) is a versatile technique to study the nanostructures. Its extreme powerful spatial resolution as well as its atomic manipulation capability enabled us to obtain the detailed information of some nano-clusters. In this thesis, I report on my studies on the noble metal (mainly Ag) clusters on the reconstructed Si(111)-(7x7) surface. / I firstly studied the fflbrication methods of the metal clusters on the Si(111)-(7x7) surface. By thermal deposition, I fabricated Ag clusters on Si(111)-( 7x7). After studying the overall growth process of the Ag clusters in half unit cells, I focused on the main target of this thesis: individual Ag clusters. By carefully observing the diffusion process of the Ag atoms on the surface, we identified of the number of atoms inside Ag3-Ag13 clusters. The STM images also showed the dynamic behaviors of each cluster, including self-hopping, dissociation and association with nearby Ag atoms. For a better controllability, a vertical manipulation technique was developed to transfer single Ag atoms across difference locations on the Si(111)-(7x7) surface. The STM tip was used to pick up or drop off metal atoms from or to the sud"ace following specific procedures. The assembly and disassembly of Ag clusters were achieved by this method. Various Ag clusters were built and the largest occupation of a FRUC was found to be 25 Ag atoms. This technique was demonstrated to be able to manipulate Au atoms and to assemble Au clusters. / With the developed fabrication methods, by thermal deposition as well as by atomic manipulation, two properties of the clusters were studied carefully: first, a prominent electrical rectifying behavior was observed for all the Ag clusters. Their individual behaviors were compared with each other. A combination of experimental measurements and first principle calculations unveiled the mechanism of the electronic rectifying behaviors to be a wave function coupling effect. The rectifying behavior for the clusters was found to persist when clusters connected laterally, whereas to disappear when the vertical size of the cluster increased to form multiple Ag layers. The second property studied is that all the clusters are found to attract nearby single Ag atoms to grow larger. This behavior plays a critical role in the growth process of the Ag clusters. we chose several typical Ag clusters and measured the merging process with single neighboring Ag atoms by atomic manipulation. The results indicate that the presence of a Ag cluster will mostly reduce the diffusion barrier of a single Ag atom in the neighboring half unit cells to diffuse to the cluster and even affect / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Ming, Fangfei = 在Si(111)-(7x7)表面的金屬納米顆粒的製備和性質 / 明方飛. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 116-122). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Ming, Fangfei = Zai Si(111)-(7x7) biao mian de jin shu na mi ke li de zhi bei he xing zhi / Ming Fangfei. / Chapter 1 --- Introduction: metal nano-clusters on semiconductor surfaces --- p.2 / Chapter 1.1 --- Background and Motivation --- p.2 / Chapter 1.1.1 --- Nano-science and nano-technology --- p.2 / Chapter 1.1.2 --- Metal nano-clusters --- p.3 / Chapter 1.2 --- Scanning tunneling microscopy (STM) --- p.6 / Chapter 1.2.1 --- Introduction to STM --- p.6 / Chapter 1.2.2 --- Basic components of STM --- p.7 / Chapter 1.2.3 --- STM working modes --- p.9 / Chapter 1.2.4 --- STM experiments in this thesis --- p.11 / Chapter 1.3 --- Substrate: the Si(111)-(7 x 7) reconstruction surface --- p.12 / Chapter 1.3.1 --- Atomic Structure --- p.12 / Chapter 1.3.2 --- Preparation in ultra high vacuum --- p.14 / Chapter 1.4 --- Growth of Ag on Si(111)-(7 x 7) at room temperature --- p.14 / Chapter 1.4.1 --- Growth method --- p.15 / Chapter 1.4.2 --- Adsorption and diffusion of single Ag atoms --- p.17 / Chapter 1.4.3 --- Forming Ag clusters --- p.20 / Chapter 1.4.4 --- Forming Ag islands --- p.23 / Chapter 1.5 --- Conclusion --- p.25 / Chapter 2 --- Individual Ag clusters: size, dynamics and stability --- p.27 / Chapter 2.1 --- Introduction --- p.27 / Chapter 2.2 --- Experiment --- p.29 / Chapter 2.3 --- Results and discussion --- p.31 / Chapter 2.3.1 --- Growth kinetics --- p.31 / Chapter 2.3.2 --- STrvr images of typical Ag structures Intra-HUC diffusion --- p.33 / Chapter 2.3.3 --- Inter-HUC diffusion --- p.37 / Chapter 2.3.4 --- Inter-HUC diffusion & identification of the number of atoms inside each cluster --- p.38 / Chapter 2.3.5 --- Stability of Ag structures. --- p.45 / Chapter 2.4 --- Conclusion --- p.49 / Chapter 3 --- Assembling and disassembling Ag/ Au clusters by atomic manipulation --- p.51 / Chapter 3.1 --- Introduction --- p.51 / Chapter 3.2 --- Experiment --- p.54 / Chapter 3.3 --- Results and disscussion --- p.55 / Chapter 3.3.1 --- Basic procedures for manipulating a single Ag atom --- p.55 / Chapter 3.3.2 --- Assembly of Ag clusters --- p.58 / Chapter 3.3.3 --- Disassembly of Ag clusters --- p.66 / Chapter 3.3.4 --- Assembly of Ag cluster patterns --- p.70 / Chapter 3.3.5 --- Comparison with the manipulation of Au atoms --- p.71 / Chapter 3.3.6 --- STrvr tip for atomic manipulation --- p.74 / Chapter 3.4 --- Conclusion --- p.75 / Chapter 4 --- Study on the electronic properties of the Ag clusters --- p.76 / Chapter 4.1 --- Introduction --- p.76 / Chapter 4.2 --- Experiment --- p.78 / Chapter 4.2.1 --- Experimental parameters. --- p.78 / Chapter 4.2.2 --- Precise tip positioning --- p.79 / Chapter 4.2.3 --- First principle calculation parameters --- p.80 / Chapter 4.3 --- Results and Discussion --- p.81 / Chapter 4.3.1 --- Grow Ag clusters --- p.81 / Chapter 4.3.2 --- I-V of the clusters. --- p.82 / Chapter 4.3.3 --- Theoretical calculation --- p.88 / Chapter 4.3.4 --- Transition from cluster to bulk in I-V. --- p.91 / Chapter 4.4 --- Conclusion --- p.94 / Chapter 5 --- Dynamics of Ag atoms near an interacting Ag cluster --- p.95 / Chapter 5.1 --- Introduction --- p.95 / Chapter 5.2 --- Results and Discussion --- p.97 / Chapter 5.2.1 --- Different Ag clusters and their orientations --- p.97 / Chapter 5.2.2 --- Association time measurement --- p.99 / Chapter 5.2.3 --- Energy barrier and diffusion prefactor --- p.101 / Chapter 5.2.4 --- Influenced intra-HUC diffusion --- p.105 / Chapter 5.2.5 --- Energy diagram --- p.107 / Chapter 5.3 --- Conclusion --- p.109 / Chapter 6 --- Conclusion and Future Work --- p.111 / Chapter 6.1 --- Conclusion --- p.111 / Chapter 6.2 --- Future work --- p.113 / Bibliography --- p.116
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328034 |
| Date | January 2012 |
| Contributors | Ming, Fangfei., Chinese University of Hong Kong Graduate School. Division of Physics. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource (ix, 122 leaves) : ill. (chiefly col.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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