臺灣博碩士論文加值系統

本研究探討以熱碳還原法在溫度900°C-1100°C及Ar流量25-400sccm下，GeO2加入WO3粉末生長WO3 nanowires(以下簡稱NWs)及Ge-Si1-xGexOy核-殼奈米線(以下以Ge-SiGeO NWs稱之)的效應。在900°C時，由熱蒸鍍或熱碳還原WO3粉末並無觀察到有奈米線生成，加入了GeO2才使得WO3 NWs 生長。 WO3奈米線生長依觀察是以氣-固機制(V-S process)成長，GeO2於其中扮演了氧化劑的角色。在此研究不同溫度下，熱碳還原法在WO3/GeO?2/C的混合粉末下生長不同種類奈米線的機制。在900°C，Ar氣氛通入1-5%氧氣的環境下會使GeO2 NWs 及WO3-GeO2 core-shell NWs 生長。而愈多的氧氣通入會抑制奈米線的成長，因為會有許多碳粉被消耗掉。 而在1050°C-1100°C下，也觀察到Ge-SiGeO NWs遵循V-S機制生長。另外，將會個別討論WO3、GeO2與Ge-SiGeO NWs的生長機制。

Effects of adding GeO2 to WO3 powders on enhancing the growth of WO3 nanowires (NWs) and Ge-Si1-xGexOy core-shell NWs ( Ge-SiGeO NWs) via the carbothermal reduction process in Ar at a flow rate of 25-400 sccm at a temperature of 900-1100°C were studied. Upon the thermal evaporation or carbothermal reduction of WO3 powders at 900°C no NWs were grown. The growth of WO3 NWs follows the vapor-solid (VS) process, where GeO2 powders act as an oxidizer. Introducing 1-5% O2 into flowing Ar enhanced the growth of GeO2 NWs and WO3-GeO2 core-shell NWs at 900°C. More O2 suppressed the growth of NWs because of the exhaustion of much graphite powders. At 1050-1100°C the growth of Ge-SiGeO NWs following the VS process were observed. In addition, the growth mechanisms of WO3, GeO2, and Ge-SiGeO NWs are discussed, respectively.

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 簡介 1
1.1 前言 1
1.2 奈米材料 2
1.3 一維奈米結構 3
第二章 文獻回顧 4
2.1 WO3及Ge介紹 4
2.2奈米線合成技術 6
2.3 奈米線生長機制 16
2.4 儀器原理 23
掃瞄式電子顯微鏡 23
掠角X光繞射儀 24
穿透式電子顯微鏡 25
X光能量散佈分析儀 26
2.5 研究動機 29
第三章 實驗步驟與方法 31
3.1 實驗設備及流程 31
3.2 基板清洗與TEM試片製備 32
基板清洗 32
TEM試片製備 33
3.3 實驗分析 33
掃瞄式電子顯微鏡分析 33
低掠角X光繞射分析 33
穿透式電子顯微鏡分析 34
陰極激發光光譜儀分析 34
第四章 結果與討論 35
4.1 WO3、GeO2奈米線及WO3-GeO2核殼奈米線之生長 35
4.2 熱碳還原WO3/GeO2粉末在Si基板上生長Ge-Si1-xGexOy核殼奈米線 39
4.3 Ge-Si1-xGexOy核殼奈米線的Cathode- luminescence(CL)分析 40
第五章 結論 42
參考文獻 43

圖目錄
圖2-1 WO3結構 50
圖2-2 Diamond cubic結構 50
圖2-3 陽極氧化鋁薄膜（AAM）的TEM影像 51
圖2-4 VLS機制示意圖 51
圖2-5 用Au作為催化劑成長Ge奈米線 (a)示意圖及Au-Ge相圖 (b)以TEM即時觀察奈米線生長情形 52
圖2-6 VLS機制和Solution-Liquid-Solid機制的比較 53
圖2-7 SFLS方法反應機構示意圖 53
圖2-8 以OAG合成Si奈米線的成核與成長示意圖 54
圖3-1 管型爐及氣體管線示意圖 55
圖3-2 粉末擺設示意圖 55
圖4-2 WO3/ GeO2/C粉末、溫度900°C、通入Ar 100sccm、在Si基板上 對WO3 nanowires的(a)TEM照片及 (b)繞射圖案 56
圖4-3 WO3/ GeO2/C粉末、溫度900°C、通入Ar 100sccm、在Si基板上
對WO3 nanorods的(a)TEM照片 (b)High resolution分析(其d值=3.78?)
(c)繞射分析 57
圖4-5 WO3/ GeO2/C粉末、溫度900°C、在Si基板上 在Ar=100sccm流量下對 WO3 nanowires的(a)(b)兩側區域 (c)(d)中央區域 SEM分析片 58
圖4-6 WO3/ GeO2/C粉末、溫度900°C、Ar=95, O2=5sccm、在Si基板上 通入氧氣後的典型生成(a)(b)為微米線SEM/EDS (c)(d)為奈米SEM/EDS 59
圖4-8 WO3/ GeO2/C粉末、溫度900°C、Ar=295, O2=5sccm、在Si基板上在通入氧氣後對WO3-GeO2 core-shell nanowires的生成 (a)(b)(c)(d)TEM及 (e)(f)EDS分析 61
圖4-9 WO3/ GeO2/C粉末、溫度900°C、Ar=295, O2=5sccm、在Si基板上 在通入氧氣後對WO3-GeO2 core-shell nanowires的生成做(a)(b)TEM為作SAED後外層變化情形 (c)外層非晶質結構的TEM照片 (d)對外殼非晶質結構high resolution分析 62
圖4-10 WO3/ GeO2/C粉末、溫度900°C、Ar=295, O2=5sccm、在Si基板上 在通入氧氣後的生成GeO2 nanowires的TEM照片及EDS分析 63
圖4-11 WO3/ GeO2/C粉末、溫度900°C、Ar=295, O2=5sccm、在Si基板上在通入氧氣後的生成WO3 nanowires的(a)TEM照片及 (b)EDS分析 64
圖4-12 WO3/ GeO2/C粉末、溫度900°C、Ar=295, O2=5sccm、在Si基板上在通入氧氣後的生成WO3 nanorods的(a)TEM照片及 (b)繞射分析 64
圖4-13 WO3/ GeO2/C粉末、溫度900°C、在Si基板上 通入不同量氧氣(a)Ar=99, O2=1sccm (b) Ar=95, O2=5sccm 的XRD分析 65
圖4-14 WO3/ GeO2/C粉末、溫度1050°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs的SEM照片 66
圖4-15 WO3/ GeO2/C粉末、溫度1100°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs的SEM照片 66
圖4-16 WO3/ GeO2/C粉末、溫度1100°C、 通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs的(a)(b)TEM及繞射照片 (c)外層EDS (d)內層EDS 67
圖4-17 WO3/ GeO2/C粉末、溫度1100°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs的TEM照片 68
圖4-19 WO3/ GeO2/C粉末、溫度1100°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs 的XRD分析 69
圖4-20 WO3/ GeO2/C粉末、溫度1100°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs 對其顆粒的(a)TEM照片及(b)EDS分析 70
圖4-20(c) WO3/ GeO2/C粉末、溫度1100°C、通入Ar 200sccm、在Si基板上生成Ge-SiGeO NWs 對應圖4-21(a)(b)所拍攝範圍的CL光譜分析 70
圖4-21 WO3/ GeO2/C粉末、溫度1050°C、通入Ar 200sccm、在Si基板上 生成Ge-SiGeO NWs 所做的CL影像分析 71

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