鈷金屬與鈷金屬氧化物奈米結構製備及其性質研究

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姓名

邊夢涵(Meng-han Bian) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

鈷金屬與鈷金屬氧化物奈米結構製備及其性質研究

相關論文

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★ 奈米尺度鎳金屬點陣與非晶矽基材之界面反應研究	★ 在透明基材上製備抗反射陽極氧化鋁膜及利用陽極氧化鋁模板法製備雙晶銅奈米線之研究
★ 準直矽化物奈米管陣列、超薄矽晶圓與矽單晶奈米線陣列轉附製程之研究	★ 尖針狀矽晶奈米線陣列及凖直鐵矽化物奈米結構之製備與性質研究
★ 金屬氧化物奈米結構製備及其表面親疏水性質之研究	★ 尖針狀鈷矽化物/矽單晶異質奈米線陣列結構之製備及其性質研究

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摘要(中)

本研究利用陽極氧化鋁奈米模板結合電化學沉積法，成功地製備出長度可調控的一維鈷金屬奈米線與奈米管，並由實驗結果觀察，奈米管管壁厚度有一梯度變化。經由場發射性質量測可得知鈷金屬奈米線與奈米管，其啟動電場分別為1.75V/μm與2.43V/μm。除此之外，我們發現鈷金屬奈米線的場增強因子(β)的數值比鈷金屬奈米管大，推測造成此現象的原因為遮蔽效應的影響。
本研究將鈷金屬奈米線分別在350℃與450℃的氧氣氛圍下進行不同熱氧化時間的處理，會因為Kirkendall effect效應製備Co3O4之串珠狀奈米管，並且利用TEM對鈷金屬氧化過程中的形貌、晶體結構與生成機制進行有系統性的研究，可知Co金屬會先轉變為CoO最終氧化成Co3O4，再利用HE-TEM觀察到CoO生成與靠近Co之處，而Co3O4位在CoO之外層。
本研究利用熱氧化法製備大面積Co3O4，並推測其成長機制為尖端生長，在氧化過程中釋放氧化層內部的應力，自然形成氧化鈷奈米線。接著以水滴接觸角量測其表面親疏水性質，並發現可以藉由真空退火、置於真空環境下以及置於一般大氣環境下，讓其表面轉變為疏水性質，並推測其機制與表面氧原子之脫附有關。

摘要(英)

In this study, we have demonstrated that length-tunable copper nanowires and nanotubes were successfully produced by using the anodic aluminum oxide (AAO) nanotemplate combined with the electrodeposition process. As the result, the wall thickness of nano tube with a gradient variations. Field emission measurements showed daturn-on fields of Co nanowire and nanotube are 1.75 V/μm and 2.43 V/μm, respectively. Moreover, the field enhancement factor(β) of Co nanowires was found to be larger than that of Co nanotubes, the result might be attributed to the so-called screen effect.
In this study, the cobalt nanowires were treated with different thermal oxidation time under oxygen atmosphere at 450℃ and 350℃.Finally, it became bead-like nanotube with kirkendall effect. We study the morphology、crystal structure and formation mechanism of Co wire during thermal oxidation with TEM. In this observation, we can tell that the sequence of the appeared cobalt oxide phase is from CoO to Co3O4, and the CoO generated at the close to the Co , and the site of Co3O4 is outside the CoO.
In this work , we fabricated the large-area Co3O4 nanowire by air oxidation of Co film .The possible mechanisms of the growth of nanowires are discussed in the context of the stress relaxation from the oxidation layer. In addition, the surface-wetting properties of the Co3O4 nanowires were evaluated by water contact angle measurements. We found that the wetting behaviors changed from hydrophilic to hydrophobic by vacuum annealing 、 placed under a vacuum environment or atmospheric environment. We speculate that this phenomenon is related to the desorption of surface oxygen atoms.

關鍵字(中)

★ 鈷金屬
★ 鈷金屬氧化物
★ 陽極氧化鋁模板

關鍵字(英)

論文目次

第一章簡介 1
1-1 前言 1
1-2 奈米材料 2
1-3 鈷金屬奈米材料………………………………………………………………………..3
1-4 鈷金屬氧化物奈米材料………………………………………………………………...4
1-5 奈米模板法……………………………………………………………………………...6
1-6 陽極氧化鋁奈米模板 …………………………………………………………………..7
1-6-1 陽極氧化鋁成長機制………...…………………………….…………………..7
1-6-2 陽極氧化鋁規則化孔洞製程………………………….…..…………………. 8
1-7奈米模板製備一維奈米結構………………………………………………………….......9
1-8 場發射電極原件…………………………………………………………………….......11
1-8-1 場發射理論……………..………………………………………..……………11
1-8-2 場發射應用……………………..……………………………………………..13
1-9 研究動機及目標………………………………………………………………………...14
第二章實驗步驟及儀器設備………………………………………………………..........15
2-1 陽極氧化鋁模板法製備一維鈷金屬奈米結構………………………………………...15
2-1-1 陽極氧化鋁模板之製程……………………………………...………….……15
2-1-2 電化學沉積法製備金屬奈米線/管陣列………...……………………………16
2-2 一維氧化鈷奈米結構製備…………………………………………………………….17
2-2-1一維氧化鈷奈米結構製備…………………………………………..............17
2-2-2氧化矽膜之銅網之製備……………………………………………………..17
2-3 大面積之氧化鈷奈米結構之製備……………………………………………………...18
2-3-1 基材使用之前處理…………………………………………………………....18
2-3-2 自組裝奈米球模板之製備……………………………………………………19
2-3-3 金屬鈷薄膜蒸鍍……………………...……………………………………....19
2-3-4 奈米球舉離及熱退火處理……....................………………………………....20
2-4實驗設備………………………………………………………………………………….20
2-4-1 蒸鍍系統(Evaporation System) ……………………....………………………20
2-4-2 氧化鋁模板製備系統………………………………....………………………20
2-4-3 電沉積系統……………………………………………………………………20
2-4-4 退火爐系統……………………………………………………………………21
2-5 儀器分析實驗…………………………………………………………………………...21
2-5-1 掃描式電子顯微鏡……………………………………………………………21
2-5-2 穿透式電子顯微鏡…………………………………………………………....21
2-5-3 高分辨穿透式電子顯微鏡(HR-TEM) ………....…………………………….22
2-5-4 真空場發射特性量測系統……………....……………………………………22
2-5-5 影像式接觸角量測儀…………………………………………………………22
第三章結果與討論………………………………………………………………………….23
3-1 陽極氧化鋁奈米模板結合電化學沉積法製備金屬奈米線/管………………………..23
3-1-1 鈷金屬奈米線/奈米管之結構分析…………………………………………...23
3-1-2 鈷金屬奈米管成長機制探討………………………………………………....25
3-2 鈷金屬奈米線/管之場發射性質量測………………………………………………......26
3-3 一維鈷金屬奈米結構之氧化機制……………………………………………………...27
3-3-1 陽極氧化鋁模板及鈷金屬奈米線形貌及結構分析…………….....…….....28
3-3-2 低溫熱氧化鈷金屬奈米線…………………………………………………..29
3-3-3高溫熱氧化鈷金屬奈米線……………………………………………………31
3-3-4 鈷金屬奈米線氧化機制探討………………………………………………..32
3-4 以熱氧化法製備氧化鈷奈米線及其成長機制探討……………...……………………34
3-4-1以熱氧化法製備大面積氧化鈷奈米線………………………………………..34
3-4-2氧化鈷奈米線成長機制探討…………………………………………………..36
3-4-3大面積氧化鈷奈米線之親疏水性質…………………………………………..36
第四章結論與未來展望…………………………………………………………………….39
4-1 結論……………………………………………………………………………………...39
4-2 未來展望………………………………………………………………………………...40
參考文獻……………………………………………………………………………………...41
圖目錄………………………………………………………………………………………...51

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指導教授

鄭紹良

審核日期

2014-8-28

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