臺灣博碩士論文加值系統

本研究應用兩階段方式，以玻璃為基板來成長高順向陣列的氧化鋅奈米線，過程中以旋轉塗佈的方式先沉積氧化鋅奈米晶粒（nanocrystals）作為成長高順向纖鋅礦結構氧化鋅奈米線（ZnO nanowires）的成核層，接著以化學溶液沉積法成長陣列的氧化鋅奈米線。實驗在低溫(90℃)環境下利用化學溶液法，將Zn(NO3)2•6H2O 和 C6H12N4在特定的實驗參數下產生反應，並過飽和析出在氧化鋅薄膜上。 此研究主要探討以溶膠凝膠法製作不同的氧化鋅成核層對於氧化鋅奈米線成長的影響，觀察所成長的氧化鋅奈米線之直徑、長度和分布密度的變化，以及探討氧化鋅奈米線在氧化鋅薄膜上的成長機制，並綜合討論成核層與氧化鋅奈米線間的相互關係。本實驗也從改變化學溶液的濃度、溫度、成長時間和pH值等，研究如何得到長徑比較高的氧化鋅奈米線。本實驗結果利用原子力顯微鏡（AFM）和掃描式電子顯微鏡（SEM）觀察氧化鋅薄膜和奈米線的表面型態，微結構方面則是藉由低掠角入射X光繞射(XRD)和高解析式電子顯微鏡(TEM)來觀測，並用光子激發光譜儀(PL)來測定其發光性質。經由本研究的結果顯示，當成核層的晶粒大小增加時，其成長的氧化鋅奈米線的平均直徑會跟著增加，而氧化鋅奈米線的分布密度與成核層表面的粗糙度、I(002)百分強度(%)和晶粒大小有關，我們亦觀察到單晶的氧化鋅奈米線是由多晶的氧化鋅成核層直接排列成長而成，且其中含有高分子的水溶液製作的成核層，所成長的氧化鋅奈米線具有較高線密度與較高順向性。本實驗研究出在化學溶液濃度範圍在20mM到30mM之間、溫度90℃下成長3到5小時，可以在固定成核層條件下成長長徑比較高且分布較均勻的氧化鋅奈米線。

A two-step process was developed to grow well-aligned ZnO nanowires on the glass substrate, which induced the pre-deposition of ZnO nanocrystals used as seeds for producing well-aligned, wurtzite ZnO nanowires arrays with spin coating and the arrayed ZnO nanowires. Those were synthesized by low-temperature chemical solution method. Aqueous solution of zinc nitrate hydrate and methenamine were used in this research. Zn(OH)2 would be supersaturated, and ZnO nanocrystals would be precipitated and grown on seed layer. In this research, we study the effect of the different kind of the seed layer synthesized by sol-gel method on the synthesis of aligned ZnO nanowires. Investigations were carried out to probe how the diameter, length, and number density of ZnO nanowires varied and the correlation between quality of ZnO nanowires and the different kinds of seed layers. And we investigated the concentration, temperature, growing time, and pH value of growing bath in order to synthesize the ZnO nanowires with high aspect ratio. We also probed into how the ZnO nanowires grew from ZnO films. Atomic force microscope (AFM) and field-emission scanning electron microscope (FESEM) were used to examine the morphology of the nanowires. The microstructure was investigated by glazing incident X-ray diffraction and high resolution transmission electron microscopy. The property of luminescence was measured by Photoluminescence (PL). The average diameter of nanowires increased with the grain size of the seed layer. The number density of nanowires was related to the roughness, the [0002] preferred orientation, and the grain size of the seed layer. The single crystal ZnO nanowires grew epitaxially from the polycrystalline seed layer directly. In addition, the ZnO nanowires grew on the seed layer fabricated with the precursor with polymer having higher alignment and number density. This study showed that we can get ZnO nanowires with higher aspect ratio and distribution-well diameter in the chemical solution with the concentration ranged from 20mM to 30mM, at temperature about 90℃, and the growing time range from 3hr to 5hr.

摘要 I
Abstract III
總目錄 V
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 研究動機及目的 3
第二章 理論基礎與文獻回顧 5
2-1 氧化鋅的基本性質與應用 5
2-1-1 氧化鋅的基本結構 5
2-1-2 氧化鋅奈米結構的應用 7
2-2 氧化鋅奈米線之合成 10
2-2-1 物理氣相法 10
2-2-2 化學氣相沈積法 [40, 41] 12
2-2-3 模板法 [9, 46] 14
2-2-4 水熱法 [47, 48] 15
2-3 在鍍有成核層的基板上以化學溶液法成長氧化鋅奈米線 18
2-3-1 以溶膠凝膠法製備氧化鋅成核層 18
2-3-2 化學溶液法成長氧化鋅奈米線 24
2-3-3 氧化鋅奈米結構成長機制 29
第三章 實驗方法與步驟 40
3-1實驗流程 40
3-2儀器設備 40
3-2儀器設備 41
3-3實驗材料 41
3-3-1 基板材料 41
3-3-2 製作成核層的化學藥品 41
3-4 實驗步驟 42
3-4-1玻璃基材清洗 42
3-4-2 Seed layer沉積條件 42
3-4-3 氧化鋅奈米線成長條件 45
3-5 分析與鑑定 45
3-5-1 表面型態觀察 45
3-5-2 薄膜結晶結構分析 46
3-5-3 微結構分析 48
3-5-4 光子激發光譜儀(PL) 49
第四章 結果與討論 50
4-1 氧化鋅成核層 (seed layer) 的特性分析 50
4-1-1 ZAD ( zinc acetate dehydrate) + NaOH之成核層-seed layer A 50
4-1-2 ZAD (zinc acetate dehydrate) + MEA (monoethanolamine) 之成核層-seed layerB 61
4-1-3 Zn (powder) + PAA (poly acrylicacid) 之成核層-seed layerC特性分析 65
4-1-4 ZAD (zinc acetate dehydrate) + PVA (polyvinylalcohol) 之成核層-seed layerD特性分析 67
4-1-5 ZNH (zinc nitrate hexahydrate) + HMT (hexamethylenetetramine) 之成核層-seed layerE特性分析 71
4-1-6 不同成核層之表面粗糙度 73
4-2 不同seed layer對氧化鋅奈米線成長之影響 82
4-2-1 seed layerA成長氧化鋅奈米線 84
4-2-2 seed layerB成長氧化鋅奈米線 95
4-2-3 Seed layerC、seed layerD及seed layerE成長氧化鋅奈米線 99
4-2-4 不同seed layer成長氧化鋅奈米線的TEM與XRD分析 103
4-3 不同熱處理條件下之seed layerA對成長氧化鋅奈米線的影響 113
4-4 不同成核層影響成長的氧化鋅奈米線之相互關係 119
4-5 相同成核層條件之不同參數反應溶液的氧化鋅表面形貌變化 124
4-5-1 反應溶液濃度變化對成長氧化鋅奈米線的影響 124
4-5-2 反應時間對成長氧化鋅奈米線的影響 130
4-5-3 反應溶液的溫度對成長氧化鋅奈米線的影響 136
4-5-4 反應溶液的pH對成長氧化鋅奈米線的影響 140
4-6 光子激發光譜分析 (PL) 151
第五章 結論 159
第六章 未來工作 162
參考文獻 164

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