本實驗使用反應性射頻磁控濺鍍法在室溫下於SiO2/Si基板上直接兩段式沈積ZnO緩衝層(Buffer Layer)與主層(Main Layer)，之後再經由不同熱退火方式製備氧化鋅奈米線。研究藉由PL、SEM、XRD及EDS分析，探討緩衝層對提升主層結晶性之作用及主層內部不同鋅、氧比例對奈米線成長之影響，而後再利用不同退火溫度探討ZnO奈米線的成長機制。
由實驗結果得知，主層內部的多餘Zn成分是提供奈米線生長所需的source來源；當退火溫度高於Zn熔點時，因熱應力所產生的擠壓作用，會將主層內部的熔融Zn推擠至薄膜表面，之後再與空氣中的O2結合形成氧化鋅奈米線。而這其中又以CTA 600℃於空氣中退火90分鐘所獲得之氧化鋅奈米線具有最佳之生長型態及密度。

In this thesis, we use reactive RF magnetron sputtering to deposit zinc oxide (ZnO) buffer layer and main layer on SiO2/Si substrate at room temperature. After various annealing treatments, the ZnO nanowires can be obtained. The effects of buffer layer on the crystallization of ZnO main layer and the zinc-to-oxygen ratio in the main layer on the growth of the ZnO nanowires are analyzed by PL, SEM, XRD and EDS. Finally, the growth mechanism of the ZnO nanowires is investigated by various annealing temperatures.
According to the experimental results, surplus zinc in the main layer is necessary for the ZnO nanowires growth. When the annealing temperature is higher than the melting point of zinc, it will melt and be extruded onto thin film surface as a result of the thermal stress. As soon as the melting zinc on the film surface reacts with the oxygen in the air, ZnO nanowires can be obtained. The optimum ZnO nanowires which possess better morphology and high density are revealed by conventional thermal annealing at 600℃ for 90 minutes.

中文摘要 Ⅰ
英文摘要 Ⅱ
誌謝 Ⅲ
目錄 Ⅳ
圖目錄 Ⅵ
表目錄 Ⅶ
第一章　前言 1
第二章　理論分析 5
2.1　奈米微粒的基本理論 5
2.1.1　量子尺寸效應 5
2.1.2　小尺寸效應 6
2.1.3 表面效應 6
2.1.4 巨觀量子隧道效應 6
2.1.5 庫倫堵塞與量子穿隧 7
2.1.6 介電限域效應 7
2.2　奈米微粒的物理特性 8
2.2.1　熱學性質 8
2.2.2　磁學性質 8
2.2.3 光學性質 9
2.2.4 力學性質 10
2.2.5 表面活性及感測特性 10
2.2.6 光催化特性 10
2.3　奈米材料 11
2.4　氧化鋅材料 13
2.4.1　氧化鋅的發光機制 13
2.4.2　氧化鋅材料之應用 13
2.5　薄膜沈積原理 15
2.6　反應性射頻磁控濺鍍原理 15
第三章　實驗 17
3.1　薄膜備製 17
3.1.1　基板清洗流程 17
3.1.2　氧化鋅濺鍍系統與薄膜沈積 18
3.2　熱處理製程 19
3.3　薄膜特性分析 19
3.3.1　掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)分析 19
3.3.2　X光繞射(X-Ray Diffraction, XRD)分析 20
3.3.3　能量分散光譜(Energy Dispersive X-ray Spectrum, EDS)分析 21
3.3.4　光致螢光光譜(Photoluminescence, PL)分析 21
第四章　結果與討論 23
4.1　氧化鋅緩衝層 23
4.1.1　微觀結構之SEM分析 23
4.1.2　結晶性之XRD分析 24
4.1.3　光特性之PL分析 25
4.2　氧化鋅主層與奈米線 25
4.2.1　濺鍍壓力之影響 25
4.2.2　氧氣濃度之影響 27
4.2.3　熱退火之影響 27
第五章　結論 33
參考文獻 35
圖　目　錄
圖2-1　氧化鋅(ZnO)結構示意圖 42
圖2-2　薄膜沈積步驟：(a)成核、(b)晶粒成長、(c)晶粒聚結、(d)縫道填補、(e)薄膜的沈積 42
圖3-1　射頻磁控濺鍍系統構造圖 43
圖3-2　射頻磁控濺鍍系統之操作流程圖 44
圖3-3　光致螢光光譜實驗系統 45
圖4-1　70%氧氣濃度及12 mtorr濺鍍壓力下沈積之ZnO緩衝層的SEM；(a)剖面圖，(b)表面圖 46
圖4-2　ZnO緩衝層之XRD分析圖 47
圖4-3　成長及無成長緩衝層之ZnO薄膜之XRD比較圖 48
圖4-4　成長及無成長緩衝層之ZnO薄膜之PL圖 49
圖4-5　未退火之ZnO主層之SEM剖面圖 50
圖4-6　退火後之ZnO主層之SEM剖面圖 50
圖4-7　退火前之ZnO主層之XRD分析圖 51
圖4-8　不同濺鍍壓力下固定21%氧氣濃度所沈積之ZnO主層經CTA退火後之SEM圖 52
圖4-9　不同濺鍍壓力下固定21%氧氣濃度所沈積之ZnO主層經CTA退火後之EDS分析圖 53
圖4-10 不同濺鍍壓力下固定21%氧氣濃度所沈積之ZnO主層經CTA退火後之鋅氧比例統計圖 54
圖4-11 不同氧氣濃度下固定3 mtorr濺鍍壓力所沈積之ZnO主層經CTA退火後之SEM圖 55
圖4-12 不同CTA退火溫度下持溫90分鐘之氧化鋅奈米線之SEM剖面圖；沈積條件為：濺鍍功率82W、氧氣濃度21%、濺鍍壓力3 mtorr 56
圖4-13 不同CTA退火溫度下持溫90分鐘之氧化鋅奈米線之XRD圖；沈積條件為：濺鍍功率82W、氧氣濃度21%、濺鍍壓力3 mtorr 57
圖4-14 不同退火溫度下之ZnO主層內部應力統計圖 58
圖4-15 利用CTA 600℃退火之ZnO奈米線成長示意圖 59
圖4-16 以CTA 600℃於空氣中退火90分鐘所生成之氧化鋅奈米線之SEM圖；(a)頂端，(b)傾斜角度 60
圖4-17 以RTA 600℃於通氧環境下退火45分鐘所生成之氧化鋅奈米絲之SEM圖 61
表　目　錄
表2-1　奈米材料的應用 62
表2-2　氧化鋅(ZnO)基本特性表 63
表3-1　反應性射頻濺鍍系統之ZnO緩衝層沈積參數 64
表3-2　反應性射頻濺鍍系統之ZnO主層沈積參數 65
表3-3　氧化鋅(ZnO)之JCPDS Data 66
表3-4　鋅(Zn)之JCPDS Data 66
表3-5　矽(Si)之JCPDS Data 67
表4-1　不同退火溫度之奈米線型態統計 68
表4-2　氧化鋅主層於不同退火溫度下所得之XRD繞射角度、平面間距與應力值 69

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