本論文主要在研究利用溶液製程－水熱法氧化鋅作為脈衝雷射沉積氮鎵的緩衝層，並利用溶液法蝕刻氧化鋅層並轉移氮化鎵薄膜至金屬基板上。
首先介紹在100mM的生長液下成長10小時可以在藍寶石基板上成長出一層結晶品質良好且C軸取向強烈的氧化鋅薄膜。
在測試脈衝雷射沉積的通入氮氣壓力與磊晶出的氮化鎵品質部分，發現在10-2 torr氮氣環境下磊晶有著最接近1:1的氮鎵元素比。然而在拍攝XRD與拉曼頻譜後發現，氮化鎵薄膜除了纖鋅礦結構外，同時還有介穩態的岩鹽結構。在提高長晶溫度至1100oC後，可以使拉曼頻譜中的纖鋅礦結構訊號出現。但是，薄膜會出現破損的情況。為了避免，我們改採以較低溫(800oC)成長氮化鎵並在以900oC退火30分鐘後，岩鹽結構轉為纖鋅礦結構。
另一部分，我們以0.25M的硫酸銅水溶液電鍍2小時得一100um厚的銅於氮化鎵/氧化鋅/藍寶石基板結構上，並以0.01M的稀鹽酸蝕刻掉氧化鋅後，將氮化鎵薄膜轉移至銅基板上。而從側面的SEM圖與EDS皆可證實氮化鎵薄膜已被成功轉移。
為了改善LED的QCSE現象，我們嘗試以水熱法製作非極性氧化鋅。在矽基板上以曝光顯影加上乾蝕刻製作出溝槽結構後，先以E-GUN鍍上金層，在旋塗氧化鋅種子層，並以水熱法成長氧化鋅奈米柱最後再以氧化還原方式除金。可在溝槽中成長出非極性面朝上的氧化鋅奈米柱。

The study of this thesis is to investigate the growth of gallium nitride (GaN) via pulsed laser deposition (PLD) on the solution processed zinc oxide (ZnO) buffer layer via hydrothermal method. After GaN growth on ZnO, we investigate the solution lift-off and transferring GaN thin film to metal substrate with ZnO layer etched by HCl solution.
In the first part of the thesis, we present the highly c-oriented and crystallinity ZnO film via hydrothermal method in the condition of 100mM solution; 90oC environment and 10 hours growth.
Next, we discover the best N2 environment of PLD-GaN growth with Ga/N ratio almost equal to 1 measured by energy dispersive spectrum (EDS). However, the Raman spectrum and the X-ray diffraction spectrum(XRD) of GaN thin film shows that the structure of GaN includes both wurzite and rock-salt structure. The rock-salt structure can be reduced by adding up the growing temperature of PLD to 1100oC. Unfortunately, crack appears on the GaN/ZnO film with over 1000oC growth.
In order to avoid cracks, GaN film is grown in a lower temperature 800oC then anneal instead. The wurzite structure signal of GaN appears in the Raman spectrum after the 900oC annealing for 30 mins.
In the other part of the thesis, we demonstrate the solution lift-off and transfer the GaN thin film to electroplating copper substrate from sapphire and confirmed it with scanning electron microscopy(SEM) and EDS.
The last part of the thesis, we propose the idea of growing non-polar ZnO on Si substrate with groove structure in order to reduce the quantum confined Stark effect (QCSE) of LED. The good step coverage of spin-coating ZnO seed layer allows us to grow ZnO nano-rods with non-polar faces on the top on the side wall of Si grooves. After removing the gold layer and the polar ZnO in the same time, we present the ZnO with non-polar face on the top.

口試委員會審定書 #
誌謝 i
中文摘要 ii
ABSTRACT iii
目錄 v
圖目錄 viii
Chapter 1 緒論 1
1.1 LED 產業現況與困境 1
1.2 垂直結構LED 7
1.3 溶液法剝離製作垂直結構LED元件 9
Chapter 2 實驗儀器與方法 12
2.1 材料簡介 12
2.1.1 氧化鋅 12
2.1.2 氮化鎵 14
2.2 水熱法簡介 14
2.3 脈衝雷射沉積 17
2.3.1 薄膜沉積原理 17
2.3.2 腔體設計 18
2.4 儀器介紹 21
2.4.1 掃描式電子顯微鏡(Scanning Electron Microscopy) 21
2.4.2 能量散射光譜儀(Energy Dispersive Spectrometer, EDS) 22
2.4.3 X光繞射儀 23
Chapter 3 以脈衝雷射沉積氮化鎵於水熱法氧化鋅 25
3.1 水熱法成長氧化鋅薄膜 26
3.1.1 實驗動機 26
3.1.2 實驗流程 27
3.1.3 量測結果與討論 29
3.2 氮化鎵薄膜成長於水熱法氧化鋅緩衝層 32
3.2.1 實驗動機 32
3.2.2 實驗設計與流程 32
3.2.3 脈衝雷射沉積磊晶氮化鎵與氮氣環境之影響 34
3.2.4 脈衝雷射沉積磊晶氮化鎵磊晶於藍寶石基板比較 36
3.2.5 脈衝雷射沉積於不同溫度磊晶氮化鎵 39
3.3 氮化鎵薄膜成長於水熱法氧化鋅與熱退火 44
3.3.1 實驗動機與設計 44
3.3.2 實驗結果 45
3.3.3 退火影響與討論 47
3.4 溶液法剝離氮化鎵薄膜 49
3.4.1 實驗動機與設計 49
3.4.2 電鍍銅基板與溶液剝離 51
3.4.3 氮化鎵薄膜轉移 52
Chapter 4 水熱法成長之非極性氧化鋅 54
4.1 研究動機 54
4.1.1 Quantum Confined Stark Effect 54
4.1.2 非極性氮化鎵 56
4.1.3 非極性氧化鋅構想 57
4.2 實驗流程 59
4.3 實驗結果與討論 61
4.3.1 氧化鋅種子層塗佈 61
4.3.2 反應性離子乾蝕刻去除極性氧化鋅 63
4.3.3 金屬剝離法移除極性氧化鋅 65
4.4 非極性氧化鋅成長於加寬溝槽 71
4.4.1 實驗動機 71
4.4.2 實驗流程 72
4.4.3 實驗結果與討論 73
4.4.4 以二階段水熱法成長氧化鋅 76
Chapter 5 結論 80
5.1 論文總結 80
5.2 未來與展望 82
Chapter 6 References 83

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