單晶矽碗狀結構及水熱法製備ZnO, AZO奈米線陣列成長動力學及其性質研究

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廖聖揚(Sheng-Yang Liou) 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

單晶矽碗狀結構及水熱法製備ZnO, AZO奈米線陣列成長動力學及其性質研究

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摘要(中)

本研究大致可以分為兩大部分，第一部分為單晶矽基板上製備碗狀凹槽結構,並討論其結構在光學抗反射上的效能。第二部分為利用濺鍍沉積之 ZnO:Al 透明導電薄膜當晶種層，成功以水熱法沉積製備 ZnO 以及 AZO 奈米線陣列，並利用 SEM、TEM、SAED、XRD、UV-Vis和EDS針對其表面形貌、成長動力學、光學特性、光暗電流、親疏水等性質作一系列研究分析。
藉由噴砂機在單晶矽表面進行噴砂，再以濕式蝕刻的方式蝕刻出碗狀結構，並定義為四個階段。藉由表面輪廓以可測得其表面粗糙度，最佳階段具有最粗糙的粗糙度，而過了最佳階段之後因碗狀結構越來越平而導致粗糙度下降。透過紫外光-可見光光譜儀量測可測得其具有非常低的反射率。
藉由TEM 和 XRD 分析可以得知本實驗水熱法製備之ZnO 和 AZO 奈米線為六方晶系纖鋅礦的單晶結構，且在本實驗之反應溫度65-80 0C內，奈米線長度和反應時間呈線性關係。藉由計算不同反應溫度下的反應速率，ZnO、AZO (2%Al) 、AZO (5%Al)和AZO(10% Al) 奈米線陣列的反應活化能可以藉由阿瑞尼士方程式推導分別為35.1(kJ/mol)、48.6 (kJ/mol)、55.6(kJ/mol)、59(kJ/mol)。濺鍍沉積AZO薄膜和AZO奈米線薄膜的電阻隨著照射UV光的時間增加而減少。此外本研究也對於ZnO材料的表面潤濕性質進行探討，且得知ZnO材料之水接觸角將會隨著放置時間的增加而變大。最後將製備完成之親水性 ZnO 與 AZO 奈米線薄膜施以真空以及氧氣氛下熱處理，可以達到調控材料表面潤濕性質之目的。

摘要(英)

There are two parts in this study, the first part is bowl-liked surface synthesis on single crystalline Si. Large area vertically-aligned ZnO and Al-doped ZnO (AZO) nanowires were successfully synthesized by hydrothermal method on glass and Si substrates in the second part. The morphologies, crystal structures, compositions, properties, and growth kinetics of the ZnO and AZO nanowires have been systematically investigated by SEM, TEM, SAED, XRD, UV-vis and EDS analyses.
Single crystalline Si was sandblasted through sandblast machine, and bowl-liked surface was manufactured successfully through wet etching. From dektak analysis, the surface roughness become larger with increasing the time of etching. The roughness will become smaller when the bowls become too large. The low reflectance was also analysised through UV-Vis.
From TEM and XRD analysis, all the ZnO and AZO nanowires synthesized were single crystalline with a hexagonal structure and their growth direction was parallel to [0001]. In addition, the lengths of the ZnO and AZO nanowires were found to increase linearly with reaction time at 65-80 0C. By measuring the growth rate at different reaction temperatures, the activation energies for the linear growth of ZnO, AZO (2%Al), AZO (5%Al) and AZO(10%Al) nanowire arrays were derived to be about 35.1、48.6、55.6、59 kJ/mol, respectively. The resistances of AZO film and AZO nanowires were measured to decrease with the exposure time of UV light. On the other hand, an abnormal surface wettability were found in the ZnO-based samples. The water contact angles of the ZnO-based tended to increase with increasing the storage days. In this study, we also demonstrate the wettability of ZnO and AZO nanowires can be modulated by annealing in vacuum and in oxygen atmosphere.

關鍵字(中)

★ 碗狀結構
★ 水熱法
★ 奈米線
★ 成長動力學

關鍵字(英)

論文目次

摘要 i
Abstract ii
致謝 iii
目錄 iv
第一章　緒論 1
1-1 前言 1
1-2 太陽能電池 4
1-2-1 矽晶太陽能電池 4
1-3透明導電薄膜表面粗糙化 5
1-4矽晶基板表面粗糙化 6
1-5透明導電材料 7
1-6氧化鋅材料 8
1-7氧化鋅摻雜鋁奈米線製備方法 8
1-8水熱法沉積ZnO奈米線合成方法以及理論基礎 9
1-9研究動機與實驗目的 11
第二章　實驗步驟 13
2-1實驗試片前處理 13
2-2化學溶液蝕刻法製備金字塔結構實驗步驟 13
2-2-1化學溶液蝕刻法製備金字塔結構 13
2-3化學溶液蝕刻法製備碗狀結構實驗步驟 14
2-3-1以噴砂機製備表面粗糙化之矽晶基板 14
2-3-2 化學溶液蝕刻法製備碗狀凹槽結構 15
2-4水熱法實驗步驟 15
2-4-1 實驗試片前處理 16
2-4-2 濺鍍沉積法製備ZnO:Al透明導電薄膜特性分析 16
2-4-3水熱法製備ZnO ，AZO奈米結構薄膜之成長動力學分析 17
2-5水熱法沉積溶液配製 17
2-6 實驗設備 17
2-6-1 濺鍍系統(Sputtering System) 17
2-6-2 水熱法沉積系統(Hydrothermal System) 18
2-6-3 真空退火系統(Vacuum Annealing System) 18
2-7 實驗分析設備 19
2-7-1 掃描式電子顯微鏡(SEM) 19
2-7-2 紫外光-可見光光譜儀(UV-VIS) 19
2-7-3穿透式電子顯微鏡與能量散佈光譜儀 20
2-7-4 XRD 繞射分析 21
2-7-5 PL光激發光譜儀 21
2-7-6 電性分析儀 22
2-7-7影像式接觸角量測儀 22
第三章　結果與討論 23
3-1 金字塔結構、碗狀結構Si之製備 23
3-2金字塔結構、碗狀結構Si之特性分析 23
3-2-1 金字塔結構、碗狀結構Si之表面形貌與反射率 23
3-2-2 改變不同參數對於其表面形貌之影響 23
3-3 水熱法沉積製備 AZO奈米線之製備與分析 25
3-3-1 不同晶種層對於水熱法沉積製備AZO奈米線之影響 25
3-3-2 溫度與時間對於水熱法沉積製備AZO奈米線薄膜之影響 25
3-3-3 水熱法沉積製備AZO 奈米線之反射率 27
3-3-4 水熱法沉積製備AZO 奈米線之TEM鑑定與分析 29
3-3-5水熱法沉積製備AZO 奈米線之XRD鑑定與分析 30
3-3-6水熱法沉積製備AZO 奈米線之PL鑑定與分析 31
3-4 水熱法沉積製備AZO奈米線之成長動力學討論 33
3-5水滴接觸角之相關原理與量測 36
3-5-1 AZO奈米線之親疏水性質及其對於電性之影響 37
3-5-2水熱法沉積製備AZO 奈米線之光暗電性分析 39
第四章　結論 41
參考文獻 44
圖目錄 52

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指導教授

鄭紹良(Shao-Liang Cheng)

審核日期

2014-8-28

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