電鍍法製備準直排列ZnO 奈米結構陣列及其特性之研究

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葉秉昀(Ping-Yun Yeh) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

電鍍法製備準直排列ZnO 奈米結構陣列及其特性之研究
(Fabrication of large-area vertically aligned ZnO nanostructure arrays by electrodeposition and their properties.)

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摘要(中)

本研究首先利用射頻磁控濺鍍系統沉積ZnO:Al透明導電薄膜作為後續電鍍沉積ZnO 奈米柱陣列之導電基材，並對此ZnO:Al導電薄膜經真空熱處理前後之晶體結構、表面形貌、顯微結構與光、電特性等方面進行探討，接著針對不同電鍍沉積ZnO 奈米柱陣列之控制參數，進行有系統的討論分析，找出大面積ZnO 奈米柱陣列之製備最佳製程參數，研究中並首度成功結合奈米球微影技術，在ZnO:Al透明導電薄膜的表面製備出具大面積碗形-蜂巢狀規則有序之ZnO 雙奈米結構。
在導電基材之ZnO:Al薄膜方面，由TEM橫截面影像可發現經真空退火熱處理前後的ZnO:Al 薄膜為多晶柱狀結構，擇優成長方向為[0001]。經真空退火後之在X光繞射圖中，其(0002)繞射峰所對應的角度位置，會明顯往高角度偏移，而在光學特性與電性上，除了光學吸收邊有藍位移現象，薄膜的電阻率也從初鍍膜之1.26 Ω-cm下降至3.0 x 10-3 Ω-cm，即結果可用Burstein–Moss現象解釋。
以電鍍沉積製備ZnO 奈米柱陣列於ZnO:Al 薄膜上之研究方面，實驗結果顯示在0.5mM的 ZnCl2 濃度和80 ℃沉積溫度，為最佳化的ZnO 奈米柱陣列生成條件，在沉積5 min與10 min ZnO 奈米柱陣列於ZnO:Al 薄膜上，不僅擁有最高光穿透率約為90 %，比平整ZnO:Al薄膜要多3-4 %，此結構也會提升光散射現象，比平整ZnO:Al 薄膜0.64 %高出1-4 %。
利用奈米球微影術製作不同大小之奈米球模板，並結合電化學沉積技術製備尺度大小可調變之碗形-蜂巢狀規則有序之ZnO 雙奈米結構，而此種具奈米雙結構之ZnO:Al透明導電薄膜，在400 nm-800 nm波長之光穿透率皆可＞80%，其在波長550 nm霧度高達17.69 %，而可見光波長範圍平均霧度也有16.37 %，遠高於ZnO:Al薄膜與ZnO 奈米柱陣列結構薄膜的霧度約10 %。

摘要(英)

In this study, ZnO:Al(AZO) transparent conducting oxide thin films were deposited on glass by a RF sputtering system to serve as the substrates for the electrodeposition of ZnO nanorods. The microstructue, surface morphology, and physical properties of the AZO thin films before and after annealing have been investigated. Large-area vertically aligned ZnO nanorod arrays were obtained under controlled electrodeposition conditions. Furthermore, bowl-like ZnO nanorod structures were successfully fabricated on AZO films by using nanosphere lithography combined with the electrodeposition technique.
According to the XTEM examinations, it is clearly revealed that the AZO films were polycrystalline and exhibited a wurtzite structure with a strong preferred [0002] orientation. From XRD & UV-VIS analyses, the (0002) peak position was found to shift toward higher angle and the optical transmittance spectra showed blue shift of annealed AZO films and their resistivity decreased from 1.26 Ω-cm to 3.0 x 10-3 Ω-cm. These observed results can be explained by Burstein–Moss effect.
In this work, the optimum electrodeposition conditions for the growth of ZnO nanorods were : 0.5 mM ZnCl2, 80 ℃, and 5–10 min. The formation of vertically aligned ZnO nanorod arrays was lead to enhance visible light transmittance and diffuse transmittances to 90 % and 2-5 % which is both higher than that of flat AZO thin films. The size and periodicity of bowl-like ZnO nanorodstructures can be controlled by turning the diameter of nanosphere and the electrodeposition conditions, In the optimum conditions, the transmittance of the ZnO nanorods sample was＞80 % in the ranges of 400-800 nm. In addition, The HAZE of the bowl-like ZnO nanorods sample is 17.7 % at 550nm wavelength, and the average HAZE in the ranges of 400-800 nm is 16.4%. These exceed the ZnO nanorod samples(＜10 %).

關鍵字(中)

★ 大面積
★ 奈米結構
★ 氧化鋅
★ 電鍍法

關鍵字(英)

★ Zinc Oxide
★ Electrodeposition
★ nanostructure
★ large-area

論文目次

目錄 I
第一章緒論(簡介) 1
1-1 前言 1
1-2 太陽光能電池 2
1-3 透明導電薄膜 2
1-4 氧化鋅薄膜 4
第二章理論基礎與文獻回顧 7
2-1 太陽能電池原理 7
2-2 透明導電金屬氧化物薄膜導電機制 9
2-3 電化學理論基礎 10
2-4 氧化鋅電化學沉積理論與機制 12
2-5 奈米球自組裝顯微影術 14
2-6 研究動機與實驗目的 16
第三章實驗步驟 17
3-1 實驗步驟 17
3-1-1 實驗試片前處理 17
3-1-2 濺鍍沉積法製備ZnO:Al透明導電薄膜特性分析 18
3-1-3 電化學沉積法製備ZnO奈米結構薄膜特性分析 18
3-1-4 電化學沉積法結合奈米球微影術製備ZnO雙奈米結構分析 18
3-2 電化學沉積溶液配置 19
3-3 實驗設備 19
3-3-1 濺鍍系統(Sputtering System) 19
3-3-2 電化學沉積設備(Electro-deposition System) 20
3-3-3 真空退火系統(Vacuum Annealing System) 20
3-4 實驗分析設備 21
3-4-1 紫外光-可見光光譜儀(UV-VIS Spectrophotometer) 21
3-4-2 XRD 繞射分析 21
3-4-3 掃描式電子顯微鏡(Scanning Electron Microscope) 22
3-4-4 穿透式電子顯微鏡(Transmission Electron Microscope) 22
第四章結果與討論 24
4-1 濺鍍沉積ZnO:Al透明導電薄膜基材之製備與分析 24
4-1-1 濺鍍法製備ZnO:Al透明導電薄膜基材之特性分析 24
4-1-2 ZnO:Al透明導電薄膜基材熱退火處理後之顯微結構分析 25
4-1-3 ZnO:Al透明導電薄膜基材熱退火處理後之光、電特性分析 27
4-2 電化學沉積ZnO 奈米結構之製備與分析 29
4-2-1 溫度對於電化學沉積製備ZnO 奈米結構薄膜之影響 29
4-2-2 濃度對於電化學沉積製備ZnO 奈米結構薄膜之影響 32
4-2-3 溶液體積對於電化學沉積製備ZnO 奈米結構薄膜之影響 35
4-2-4 時間對於電化學沉積製備ZnO 奈米結構薄膜之變化 37
4-3 大面積規則ZnO:Al雙奈米結構之製備與分析 39
4-3-1 ZnO:Al 透明導電薄膜基材上製備規則奈米球陣列 39
4-3-2奈米球微影術結合電化學沉積製備ZnO 雙奈米結構即其特性分析 40
4-3-3 二維 ZnO 雙奈米結構之光特性分析 43
第五章結論 46
參考文獻 48
圖目錄表目錄 54
參考文獻圖目錄 58

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指導教授

鄭紹良(Shao-Liang Cheng)

審核日期

2010-7-28

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