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研究生：	洪琪祐 Hong, Chi-yew
論文名稱：	經由熱蒸鍍法以銀及銅催化Ge奈米結構的生長 Ag- and Cu-catalyzed growth of Ge nanostructures by the thermal evaporation method
指導教授：	林文台 Lin, Wen-Tai
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2008
畢業學年度：	96
語文別：	中文
論文頁數：	75
中文關鍵詞：	Ge 奈米結構、銀催化
外文關鍵詞：	Ag-catalyzed, Ge nanostructures
相關次數：	點閱：47 下載：3
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本研究探討在950˚C氬氣環境中熱蒸發 Ge 粉末，銀催化生長直的 Ge 奈米線，鋸齒狀的 Ge 奈米帶與六邊形的 Ge 奈米塔。在550-600˚C生長 Ge奈米線與 Ge 奈米帶係經由VSS機制以 top-growth 模式生長而在700-750˚C 生長 Ge 奈米塔係經由 VLS 機制以 bottom-growth 模式生長。這些結果顯示銀催化生長 Ge 奈米結構的生長模式與溫度相關。同時也討論Ge 奈米結構的生長機制。Ge奈米線、Ge 奈米帶與Ge奈米塔分別偏好 <110>、<112> 與 <111> 生長方向。表面能、界面能與動力的影響係決定 Ge 奈米結構生長的重要因素。也探討在950˚C氬氣環境中，經由熱蒸發 Ge 粉末以銅催化生長 Ge 奈米線。Ge 奈米線在500-600˚C經由 VSS 機制以 top-growth 模式生長。

The Ag-catalyzed growth of straight Ge nanowires (GeNWs), serrate Ge nanobelts (GeNBs), and hexagonal Ge nanotowers (GeNTs) by the thermal evaporation of Ge powder at 950˚C in Ar were studied. The top-growth mode was found for the growth of GeNWs and GeNBs at 550-600˚C via the vapor-solid-solid (VSS) process, while the bottom-growth mode was found for that of GeNTs at 700-750˚C via the vapor-liquid-solid process. This result shows that the growth mode for the Ag-catalyzed Ge nanostructures is temperature-dependent. The large size of AgGe droplets formed at high temperatures is beneficial to the growth of GeNTs with the bottom-growth mode. In addition, the growth mechanisms of Ge nanostructures are discussed. The GeNWs, GeNBs, and GeNTs favored the <110>, <112>, and <111> growth orientations, respectively. The surface energy, interfacial energy, and kinetic effect are important factors in determining the growth direction of Ge nanostructures. The Cu-catalyzed growth of GeNWs by the thermal evaporation of Ge powder at 950˚C in Ar was also studied. The top-growth mode was also found in the growth of GeNWs at 500-600˚C via the VSS process.

本文目錄
中文摘要..................................................I
英文摘要.................................................II
誌謝感言................................................III
本文目錄.................................................IV
圖目錄...................................................VI
第一章  奈米材料..........................................1
1.1前言...................................................1
1.2一維奈米材料...........................................3
第二章   文獻回顧.........................................6
2.1 一維奈米材料合成方式..................................6
熱蒸鍍 (thermal evaporation)..............................6
化學氣相沉積（chemical vapor deposition）.................7
熱碳還原（carbothermal reduction）........................9
水熱(Solvothermal)	.......................................10
雷射蒸鍍（laser ablation）...............................11
模板輔助（template-assisted）............................11
溶膠-凝膠（sol-gel）.....................................11
2.2 奈米線生長機制	.......................................12
Vapor-Liquid-Solid（VLS）................................13
Vapor-Solid（VS）........................................15
Vapor-Solid-Solid (VSS)..................................17
Oxide-Assisted Growth（OAG）.............................18
Solution-Liquid-Solid(SLS、SFLS、SFSS)...................19
2.3 奈米線生長模式	.......................................20
2.4 儀器原理.............................................21
2.4.1 掃瞄式電子顯微鏡（Scanning Electron Microscope，SEM）....................................................21
2.4.2 掠角X光繞射儀（Grazing Incidence X-ray Diffractometer，GID）....................................23
2.4.3 穿透式電子顯微鏡（Transmission Electron Microscope，TEM）....................................................24
2.4.4 X光能量散佈分析儀（Energy Dispersive X-ray Spectrometer，EDS）......................................25
2.5 研究動機.............................................26
第三章  實驗步驟與方法...................................29
3.1 實驗設備及流程.......................................29
3.2 基板製備與清洗與TEM試片製備..........................30
3.2.1基板製備與清洗......................................30
3.2.2 TEM試片製備........................................31
3.3 實驗分析.............................................32
3.3.1掃瞄式電子顯微鏡分析................................32
3.3.2 低掠角X光繞射分析..................................32
3.3.3 穿透式電子顯微鏡分析...............................33
第四章  結果與討論.......................................34
4.1 Ge 奈米結構的生長機制................................34
4.2 影響 Ge 奈米結構的生長方向與形貌的因素...............38
4.3銅催化生長Ge奈米線....................................40
第五章  結論.............................................43
參考文獻.................................................44

圖目錄
圖2-1. VLS示意圖.........................................50
圖2-2(a).用Au做催化劑生長Ge奈米線示意圖..................50
圖2-2(b)..Au-Ge相圖......................................50
圖2-2(c).以TEM即時觀察影像圖.............................51
圖2-3.以OAG合成Si奈米線的成核與成長示意圖................51
圖2-4. SiOx NWs銅膜厚度60nm，銅膜會變成cluster-like(叢聚)的結構，且SiOx的核會變成塊狀(agglomeration)................52
圖2-5. VLS機制和Solution-Liquid-Solid機制的比較..........52
圖2-6. SFLS方法反應機構示意圖............................53
圖2-7. SFSS方法反應機構示意圖............................53
圖2-8. 生長模式示意圖....................................54
圖3-1 高溫爐與試片擺設位置示意圖.........................55
圖3-2. 下游試片擺設位置示意圖............................55
圖3-3. 實驗流程示意圖....................................56
圖4-1.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，純Si基板擺在溫度550~600℃上生成物之SEM影像圖.................57
圖4-2. Si基板上沉積的Ag顆粒之SEM影像圖...................57
圖4-3.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃上所生成的奈米線之SEM影像圖.......58
圖4-4.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃上的生成物之XRD分析圖.............58
圖4-5.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃上所生長的<110>方向奈米線之TEM影像圖及繞射圖.................................................59
圖4-6.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃， (a)生長的奈米線之TEM影像圖， (b)在圖(a)所圈選位置之EDS能譜圖.............................59
圖4-7.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃， (a)生長的<112>方向奈米帶之TEM影像圖， (b)在圖(a)較下方標示為(b)的奈米線，靠近頭部之TEM影像圖， (c)在圖(b)中，其頭部顆粒之EDS能譜圖.................60
圖4-8.在圖4-7(a)中較下方標示為(b)的奈米線，靠近尾部之區域，(a)放大之TEM影像圖 (b)在圖(a)的1位置之EDS能譜圖， (c)在圖(a)的2位置之EDS能譜圖， (d)在圖(a)的3位置之EDS能譜圖， (e)在圖(a)的4位置之TEM繞射圖， (f)在圖(a)的5位置之TEM繞射圖.......................................................62
圖4-9.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃所生長的<112>方向奈米帶之TEM影像圖及其繞射圖.................................................63
圖4-10. Ag-Ge相圖........................................63
圖4-11. Ag顆粒尺寸大小對應熔點下降關係圖.................64
圖4-12.粉末溫度950℃，氬氣流量100 sccm，持溫時間60min，Ag／Si基板擺在溫度550~600℃上所生長的奈米線之TEM影像圖.......64
圖4-13.粉末溫度950℃，氬氣流量100 sccm，持溫時間60min，Ag／Si基板擺在溫度550~600℃上所生長的奈米線之TEM影像圖.......65
圖4-14.粉末溫度950℃，氬氣流量100 sccm，持溫時間30 min，Ag／Si基板擺在溫度550~600℃， (a)生長的奈米線之SEM影像圖， (b)高倍 SEM影像圖........................................65
圖4-15.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度550~600℃， (a)生長＜112＞方向的奈米帶之TEM影像圖， (b)為圖(a)的奈米帶之[111]方向繞射圖， (c)為圖(a)的奈米帶之[011]方向繞射圖..................................66
圖4-16.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度700~750℃上， (a)生長的奈米塔之SEM影像圖， (b)為圖(a)奈米塔之SEM影像放大圖，內插圖為尖端局部放大圖.......................................................67
圖4-17.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度700~750℃上所生長＜111＞方向的奈米塔之TEM影像圖及其繞射圖...........................................68
圖4-18(a) 粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Ag／Si基板擺在溫度700~750℃， (a)生長的奈米線之TEM影像圖， (b)在圖(a)上頭部圈選位置的EDS能譜圖......................68
圖4-19.粉末溫度950℃，氬氣流量100 sccm，持溫時間30 min，Ag／Si基板擺在溫度700~750℃， (a)生長的奈米線之SEM影像圖， (b)在圖(a)上A位置的EDS能譜圖， (c)生長的奈米線之SEM影像圖， (d)在圖(c)上B位置的EDS能譜圖........................69
圖4-20. [110]方向生長的奈米線............................70
圖4-21.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度500~600℃， (a)生長的奈米線的SEM影像圖， (b) 為圖(a)之SEM影像放大圖...............................70
圖4-22.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度500~600℃，生成物的XRD分析圖.............71
圖4-23. Cu-Ge相圖........................................71
圖4-24.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度660~750℃， (a)生長的奈米線的SEM影像圖， (b)為圖(a)之SEM影像放大圖................................72
圖4-25.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度500~600℃， (a)生長的奈米線的TEM影像圖， (b)在圖(a)上1位置之EDS能譜圖， (c)在圖(a)上2位置之EDS能譜圖， (d)在圖(a)上3位置之EDS能譜圖， 
(e)在圖(a)上4位置之EDS能譜圖， (f)在圖(a)上5位置之EDS能譜圖.......................................................73
圖4-26.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度500~600℃， (a)生長的奈米線的TEM影像圖， (b)為圖(a)奈米線的TEM繞射圖..............................74
圖4-27.粉末溫度950℃，氬氣流量100 sccm，持溫時間60 min，Cu／Si基板擺在溫度500~600℃， (a)生長的奈米線之TEM影像圖， (b)為圖(a)奈米線的high-resolution高解析圖................75
                                    

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