水熱法製備ZnO, AZO 奈米線陣列成長動力學以及性質研究

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徐菁鴻(Ching-Hung Hsu) 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

水熱法製備ZnO, AZO 奈米線陣列成長動力學以及性質研究

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摘要(中)

本研究利用射頻磁控濺鍍系統沉積 ZnO:Al (AZO)透明導電薄膜作為晶種層，
成功的以水熱法製備出一系列長短寬度可調變之純 ZnO 以及 AZO 奈米線陣列，
利用 SEM、TEM、SAED、XRD、UV-vis 和EDS 針對其晶體結構、表面形貌、
光電性質和表面潤濕性質進行一系列深入的觀察與分析。
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) 和 AZO (5%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36.3 ( kJ /mol ) 、49.2 ( kJ / mol ) 和45.2 ( 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)

In this study, large area vertically-aligned ZnO and Al-doped ZnO (AZO)
nanowires were successfully synthesized by hydrothermal method o glass and Si
substrates. 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.
From TEM and XRD analyses, 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), and AZO (5%Al) nanowire arrays were derived to be about 36.6, 49.2 and
45.2 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 AZO, and Zno nanowires can be
modulated by annealing in vacuum and in oxygen atmosphere.

關鍵字(中)

★ 水熱法
★ 氧化鋅

關鍵字(英)

★ hydrothermal method
★ ZnO

論文目次

摘要............................................................................................................. I
Abstract .....................................................................................................II
致謝.......................................................................................................... III
目錄.......................................................................................................... IV
圖目錄..................................................................................................... VII
第一章緒論 ............................................................................................ 1
1-1 前言 .............................................................................................. 1
1-2 太陽能電池 .................................................................................. 2
1-3 透明導電材料 .............................................................................. 3
1-4 氧化鋅材料 .................................................................................. 5
1-5 金屬氧化物透明導電材料導電機制 .......................................... 6
1-6 一維ZnO 奈米線成長機制與製備方法 .................................... 7
1-6-1 氧化鋅摻雜鋁奈米線製備方法 ......................................................... 8
1-7 水熱法沉積ZnO 奈米線合成方法以及理論基礎 .................... 8
1-8 氧化鋅的潤濕性質 .................................................................... 10
1-9 研究動機與實驗目的 ................................................................. 13
第二章實驗步驟 .................................................................................. 15
V
2-1 實驗步驟 .................................................................................... 15
2-1-1 實驗試片前處理 ............................................................................... 15
2-1-2 濺鍍沉積法製備ZnO:Al 透明導電薄膜特性分析 ....................... 15
2-1-3 水熱法製備ZnO ，AZO 奈米結構薄膜之成長動力學分析 ....... 16
2-2 水熱法沉積溶液配製 ................................................................ 16
2-3 實驗設備 .................................................................................... 17
2-3-1 濺鍍系統(Sputtering System) ......................................................... 17
2-3-2 水熱法沉積系統(Hydrothermal System) ...................................... 17
2-3-3 真空退火系統(Vacuum Annealing System) .................................. 17
2-4 實驗分析設備 ............................................................................ 18
2-4-1 紫外光-可見光光譜儀(UV-VIS) ..................................................... 18
2-4-2 XRD 繞射分析 ................................................................................. 19
2-4-3 掃描式電子顯微鏡(SEM)................................................................ 19
2-4-4 穿透式電子顯微鏡(TEM) ............................................................... 19
2-4-5 高分辨穿透式電子顯微鏡(HR-TEM)與能量散佈光譜儀(EDS) . 20
2-4-6 影像式接觸角量測儀 ....................................................................... 21
2-4-7 電性分析儀 ....................................................................................... 21
第三章結果與討論 .............................................................................. 22
3-1 濺鍍沉積 ZnO:Al 透明導電薄膜基材之製備與分析 .......... 22
3-1-1 濺鍍法製備 ZnO:Al 透明導電薄膜之相鑑定與特性分析 ......... 22
3-1-2 ZnO:Al 透明導電薄膜真空熱處理前後特性分析 ........................ 23
3-2 水熱法沉積製備 AZO ，ZnO 奈米結構之製備與分析 ..... 26
3-2-1 溫度對於水熱法沉積製備AZO ，ZnO 奈米結構薄膜之影響 .. 26
VI
3-2-2 時間對於水熱法沉積製備AZO，ZnO 奈米結構薄膜之影響 .... 29
3-2-3 水熱法沉積製備ZnO ，AZO 奈米線之鑑定 ............................. 32
3-3 水熱法沉積製備ZnO ，AZO 奈米線之成長動力學討論 ... 33
3-4 AZO 奈米結構光暗電性質分析 ................................................ 35
3-5 ZnO 和AZO 奈米結構之親疏水性質討論 .......................... 37
第四章結論 .......................................................................................... 40
參考文獻 .................................................................................................. 43

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指導教授

鄭紹良(S. L. Cheng)

審核日期

2013-8-27

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