臺灣博碩士論文加值系統

本研究藉由鎳/鍺、金/鈦之核殼奈米粒子進行固態反應來形成中空鍺化鎳、金鈦化合物化物奈米球殼，並利用臨場超高真空穿透式電子顯微鏡來觀察形成中空奈米球殼的反應過程。首先，利用電子束微影系統以及電子槍蒸鍍系統，將鎳/鍺核殼奈米結構製備於穿透式電子顯微鏡觀察用的氮化矽薄膜窗口試片上，此外亦藉由電子槍沉積系統鍍覆金薄膜於氮化矽薄膜窗口試片背面的二氧化矽側，並使用快速退火系統900℃下加熱10分鐘形成金奈米粒子，接著沉積鈦薄膜包覆所形成之金粒子來製備出金/鈦核殼奈米粒子。當此兩種核殼奈米粒子分別於450℃與600℃以上加熱時，因其核殼材料界面間的非平衡交互擴散，即為柯肯道爾效應，使得在內部具較大擴散係數的材料上產生空孔，並隨著反應的進行而逐漸形成中空形貌之金鈦化合物奈米球殼或是內部有鎳剩餘的鍺化鎳奈米球/殼結構。最後，由本研究中臨場加熱所觀察到的擴散行為，以及後續對形成的中空奈米結構所做的顯微結構、晶格結構、元素分布等分析，我們提出具有不同尺寸核顆粒的核殼奈米結構，其各自透過柯肯道爾效應來製備中空奈米結構的擴散機制。

In this work, we demonstrate the formation of hollow Ni germanide and AuTi compound nanospheres by a solid state reaction of Ni/Ge and Au/Ti core/shell nanoparticles, respectively. The structural evolution of hollow AuTi compound and Ni germanide nanospheres have been investigated in real-time ultrahigh vacuum transmission electron microscopy (UHV-TEM). When annealed above 450℃, the non-equilibrium counter-diffusion of core and shell species occurred through an interface. Therefore, Ni germanide and AuTi compound hollow nanospheres were formed by a solid state reaction involving the Kirkendall effect. Finally, we propose the mechanism with the effects of the size and annealing duration on solid state reaction based on the Kirkendall effect. And it can look forward to the application in the fabrication of other system with different hollow morphologies according to the mechanism proposed in this study.

摘要 I
Abstract II
致謝 III
目錄 IV
List of Acronyms and Abbreviations XII
第一章 前言 1
第二章 文獻回顧 3
2-1 奈米科技 3
2-2中空結構奈米材料合成方法介紹 4
2-2-1傳統模板法(conventional templates) 4
2-2-1-1逐層組裝法(layer-by-layer assembly) 5
2-2-1-2直接化學沉積法(direct chemical deposition) ....................................6
2-2-1-3表面化學吸附法(chemical absorption on surface layer) 7
2-2-1-4 軟性模板法(soft-templating method) 7
2-2-2奈米尺度之柯肯道爾效應(nanoscale Kirkendall effect) 9
2-2-3伽凡尼取代(galvanic replacement) 10
2-2-4化學蝕刻(chemical etching) 11
2-3 中空奈米結構的應用與發展 13
2-3-1 生物醫學的應用(biomedical applications) 13
2-3-2 鋰離子電池(lithium-ion batteries) 13
2-3-3 氣體感測器(gas sensing) 14
2-3-4 光催化(potocatalysis) 15
2-4 研究動機 15
第三章 實驗方法與步驟 23
3-1 實驗步驟 23
3-1-1 製備氮化矽薄膜窗口試片 23
3-1-2 製備鎳/鍺核殼奈米粒子 23
3-1-3 製備鎳/鍺核殼奈米粒子橫截面 24
3-1-4製備金/鈦核殼奈米粒子 24
3-1-5 臨場加熱形成中空奈米結構 24
3-1-5 核殼奈米結構及中空奈米結構形貌觀察與結構鑑定 24
3-2 實驗儀器介紹 25
3-2-1 形貌觀察及結構鑑定 25
3-2-1-1. 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 25
3-2-1-2. 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 26
3-2-2. 試片製備 26
3-2-2-1 電子束微影系統(E-beam lithography) 26
3-2-2-2 電子槍蒸鍍系統(E-beam evaporator) 26
3-2-2-3 聚焦離子束系統(Focused Ion Beam System) 27
第四章 結果與討論 32
4-1 鎳/鍺核殼奈米粒子 32
4-1-1 形貌分析 32
4-1-2顯微結構分析 32
4-2鍺化鎳中空奈米粒子 33
4-2-1顯微結構分析 33
4-2-2結晶結構分析 34
4-2-3元素分布分析 34
4-2-4形成鍺化鎳中空奈米粒子的臨場加熱觀察 35
4-3鎳/鍺核殼結構橫截面試片 36
4-3-1鎳/鍺核殼結構橫截面試片臨場加熱觀察 36
4-3-2鍺化鎳中空結構橫截面試片結晶結構分析 37
4-4金/鈦核殼奈米粒子 38
4-4-1顯微結構分析 38
4-4-2結晶結構分析 39
4-5金鈦化合物中空奈米粒子 39
4-5-1顯微結構分析 39
4-5-2結晶結構分析 39
4-5-3元素分布分析 40
4-6擴散機制探討 40
第五章 結論與未來展望 57
5-1 結論 57
5-2 未來展望 58
參考文獻 59

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