臺灣博碩士論文加值系統

有關於奈米結構或奈米元件甚至於分子元件已廣泛地被討論，這是因為他們可被使用於發展新一代的電腦晶片。其中，由於奈米線可作為微電腦的資料傳輸導線，所以其製備過程更是備受注目，這最終的目標是製備原子級的金屬導線。近年來已有金屬串鏈錯合物被合成出來，這類具有不同中心的金屬原子及不同鏈長的錯化分子的獨特應用潛力，吸引我們去研究其在半導體表面的化學反應，以更進一步瞭解製備原子級金屬導線的過程。在此研究中，三核的金屬鏈錯合物Cr3(μ3-dpa)4Cl2(dpa=dipyridylamido anion)被作為固體表面金屬鏈前驅物，並暴露於GaN(0001)和Si(100)表面上，隨後的化學反應以程溫脫附法、歐傑電子能譜法、同步輻射X-光電子能譜術以及二次離子質譜法來監測。此金屬串鏈分子在低溫吸附於GaN表面上時，是經由Cr原子與GaN樣品表面鍵結。在暴露量為50L時， GaN(0001)表面上可能有兩層金屬串鏈分子層，第一層分子以似圓盤形狀躺於表面上，第二層分子則似圓盤形狀站立的方式吸附於第一層上方。隨著GaN表面溫度的增加，此錯合物在兩個不同的階段分別解離，在約340K時有配位基分子從錯合物中脫附出來，而在約540K時殘餘的錯合物會進一步解離。在高溫的表面溫度下暴露大量的金屬串鏈錯合物，鉻的金屬層成長以及微量的鉻金屬的雙原子聚合可被觀測。在金屬串鏈分子與Si(100)表面的反應研究中，顯示低溫下即有配位基解離至表面上，持續的加溫會使得配位基更進一步解離。在較高暴露量下，當表面溫度為280K時，有配位基分子將解離脫附出表面，而在表面溫度為400K和490K時，解離的CrxLy的分子會脫附出表面。

The research focused on nanostructures, nanodevices and even on molecular devices has been extensively carried out due to their potential applications in fabrication of computer chips. Among them, the fabrication process of the nanowire has drawn great attention because of its use as the data-transfer line in the nano-scale. The ultimate goal is to fabricate the atomic-scale metal wire on the surface. The recent success in the synthesis of the linear metal-chain complexes with various nuclear chain lengths has stimulated us to study the chemical reaction between this kind of compounds and the semiconductor surface in order to obtain insights into the process which may govern the fabrication of the atomic-scale metal wire on surfaces. In this study, a tri-nuclear metal string complex Cr3(μ3-dpa)4Cl2 (dpa=dipyridylamido anion) is used as the precursor and deposited on GaN(0001) and Si(100) surface in a UHV environment. Their surface chemical reactions are monitored using temperature programmed desorption, Auger electron spectroscopy, synchrotron radiation core-level spectroscopy, and secondary ion mass spectroscopy. At low temperature, the layer of adsorbates might be formed through Cr bonding to the surface. At an exposure of 50L, there may be two adlayers on the GaN(0001) surface, the first one binding with a configuration similar to the molecular dish laying flat on the surface, the second one with the dish standing up. At increasing substrate temperatures, the complex decomposes in two different stages. One relates to the desorption of the dpa ligand from the adsorbed complex at ~340K, the other to a further decomposition of the residual complex at ~540K. A Cr metal adlayer, containing mainly Cr adatoms with a trace amount of Cr dimers, can be obtained when the metal-string complex is exposed to the GaN surface at high substrate temperature above 770K. In the case of Cr3(μ3-dpa)4Cl2 reaction on the Si(100) surface, the ligand on the complex decomposes upon adsorption on the surface. At increasing substrate temperature, further decomposition of the ligand will occur. At a higher exposure, the ligand molecule can desorb at a substrate temperature of 280K and the decomposed CrxLy molecule will desorb from the Si(100) surface at the temperature of 400K and 490K.

第一章緒論
1.1 電腦的發展過程 1
1.2.1分子電腦Teramac 3
1.2.2 分子邏輯閘 4
1.2.3 網狀線路與缺陷偵測 5
1.2.4 864 晶片與Teramac 5
1.2.5 化學電腦 6
1.3.1 奈米技術(nanotechnology) 7
1.3.2奈米線(nanowire)之發展 9
1.4.1 金屬串鏈分子 12
1.4.2 [Cr3(dpa)4Cl2] 金屬串鏈分子之結構分析 16
1.5 磊晶成長與基材之晶格匹配 18
1.6.1 新世代半導體光電材料－氮化鎵(GaN)之發展 19
1.6.2 GaN(0001)面 22
第二章實驗儀器、原理與步驟
2.1 超高真空系統 25
2.2 樣品處理與清潔過程 28
2.2.1 [Cr3(dpa)4Cl2]金屬串鏈分子合成過程 28
2.2.2 金屬串鏈分子之分析 28
2.2.3 [Cr3(dpa)4Cl2]金屬串鏈分子樣品置入超高真空系統之前處理過程 32
2.2.4 GaN(0001)表面之清潔處理 33
2.2.5 Si(100)表面之清潔處理 33
2.2.5 金屬串鏈分子暴露量之校正 35
2.3 實驗中所使用之表面分析技術 37
2.3.1低能電子繞射儀(LEED) 37
2.3.2歐傑電子能譜儀(AES) 37
2.3.3程溫脫附法(TPD) 37
2.3.4二次離子質譜法 (SIMS) 38
2.3.5軟X光光電子能譜法(SXPS) 39
第三章、實驗結果與討論
3.1金屬串鏈分子[Cr3(dpa)4Cl2]於GaN(0001)表面程溫脫附實驗 41
3.2 SIMS 二次離子質譜分析 49
3.2.1低溫吸附金屬串鏈分子[Cr3(dpa)4Cl2] 49
3.2.2 低暴露量下時，isotope pyridine、Hdpa和金屬串鏈分子 [Cr3(dpa)4Cl2]之二次離子質譜 51
3.2.3隨溫度升高之二次離子質譜圖 54
3.3 X光電子能譜圖 60
3.3.1-1低溫下隨暴露量增加之N1s XPS 60
3.3.1-2隨表面溫度增加之N1s XPS 63
3.3.2-1低溫下隨暴露量增加之C1s XPS 65
3.3.2-2隨表面溫度增加之C1s XPS 68
3.3.3-1低溫下隨暴露量增加之Cr3p XPS 70
3.3.3-2隨表面溫度增加之Cr3p XPS 74
3.3.4-1低溫下隨暴露量增加之Cl2p3/2 XPS 77
3.3.4-2隨表面溫度增加之Cl2p3/2 XPS 80
3.3.5-1低溫下隨暴露量增加之Ga3d5/2 XPS 82
3.3.5-2隨表面溫度增加之Ga3d5/2 XPS 85
3.3.6能量鋒面積隨暴露量之變化與分子位向之討論 87
3.4利用金屬串鏈分子作為製成金屬薄膜之前驅物，以高曝量與高溫表面的環境下，模擬Cr原子之磊晶過程 91
3.4.1初始表面溫度為280K 91
3.4.2初始表面溫度為450K 93
3.4.3初始表面溫度為770K 97
3.4.4高溫、高暴露量下之Cr金屬磊晶成長之討論 98
3.5.1 金屬串鏈分子[Cr3(dpa)4Cl2]於Si(100)表面程溫脫附實驗 100
3.5.2 金屬串鏈分子[Cr3(dpa)4Cl2]與Si(100)表面反應之二次離子質譜分析 111
3.5.2.1 隨暴露量增加下，低溫吸附金屬串鏈分子[Cr3(dpa)4Cl2] 111
3.5.2.2隨溫度升高之二次離子質譜圖 113
第四章 結論
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