臺灣博碩士論文加值系統

本研究分為兩個階段製程，第一階段是製作氧化鋅準直奈米柱，先利用PLD在sapphire基板上製作約68nm氧化鋅緩衝層，再利用氣相傳輸法在緩衝層上成長氧化鋅準直奈米柱。並利用SEM觀察表面結構，奈米柱直徑約30±5nm、長約1.3 μm，經XRD觀察成長方向為[0002]，PL強度與結晶品質良好且沒出現DLE。
第二階段是使用氧化鎂(4N8)與氧化鋅(4N5)莫爾比1:10與1:4混合製成氧化鎂鋅靶材，利用PLD鍍氧化鎂鋅以包覆氧化鋅準直奈米柱，使結構成為core-ZnO/shell-MgZnO異質奈米柱。在僅改變雷射發數條件下，利用HRTEM觀察其氧化鎂鋅外殼的厚度變化，殼層的晶格常數介於氧化鎂與氧化鋅之間，驗證出殼層為MgxZn1-xO單晶相。利用PL量測得知氧化鋅(3.298eV)、(1:10)mol% MgxZn1-xO(~3.594eV )與(1:4)mol% MgxZn1-xO( ~3.935eV )。從TEM與PL量測下，根據計算可得到前者成分比為x=0.14而後者為x=0.3。隨著雷射發數的增加，MgxZn1-xO的峰值越趨顯著，故我們可藉由控制殼層厚度達到控制MgxZn1-xO光激發受激輻射的放光強度。

The formation of heterostrucure in nanorods is essential for their potential applications in nanoelectronic and photonic devices. Here we demonstrate that vertically well-aligned ZnO nanorods and ZnO/MgZnO core-shell nanorods can be successfully synthesized via catalyst-free vapor phase transport combined with pulsed laser deposition (PLD) method.
The thesis consists of two parts. First, the vertically well-aligned ZnO nanorods were grown on a PLD-predeposited ZnO thin film via a simple thermal evaporation and vapor transport process. These ZnO nanorods were quite uniform with a diameter of ~27 nm and length of ~1 μm. Room-temperature photoluminescence spectra of the samples showed only a strong band-edge emission, indicating the high crystalline quality. The well-aligned ZnO nanorods were used as a template for the synthesis of nanorod heterostructures.
In the second part, the vertically well-aligned ZnO/MgZnO core-shell structures of the nanorods were synthesized by PLD of MgZnO onto the ZnO nanorod template. The core-shell heterostructure nanorods were examined by high-resolution transmission electron microscopy measurements. The optical properties of the heterostructure nanorods were analyzed by photoluminescence. The HRTEM images and the corresponding FFT patterns of the nanorods implied that the core/shell is wurtzite structured ZnO/MgZnO with well-defined epitaxial relationship. The positions of the MgxZn1-xO shells, obtained by pused laser ablating MgyZn1-yO targets with y=0.0909 and 0.25, were determained by the Vegard’s law to be x=0.14 and 0.30, respectively. Room-temperature PL spectrum from the ZnO/MgxZn1-xO core-shell nanorods exhibits strong emissions from ZnO core (located at 3.298eV) and MgxZn1-xO shell (located at 3.539eV for x=0.14 and 3.935eV for x=0.30). The core/shell relative emission intensity can be controlled by the shell thickness.

摘　要 i
英文摘要 ii
誌 謝 iii
第一章 緒論 1
1.1 前言 1
1.2 文獻回顧 2
1.2.1 氧化鋅奈米結構 2
1.2.2 氧化鋅光學特性 6
1.2.3 氧化鎂鋅奈米結構介紹 9
1.3 研究動機 14
第二章 材料簡介與製程方法原理 15
2.1 實驗材料介紹 15
2.1.1 氧化鋅(Zinc Oxide, ZnO)結構與特性 15
2.1.2 氧化鎂鋅(MgZnO)結構與特性 16
2.2 一維奈米結構成長機制 18
2.2.1 氣-液-固成長(vapor-liquid-solid mechanism, VLS) 18
2.2.2 氣-固成長(vapor-solid mechanism, VS) 19
2.2.3 碳熱還原反應 19
2.2.4 脈衝雷射蒸鍍法(pulsed laser deposition, PLD) 20
2.3 TEM之晶格成像原理與晶格指數分析 21
2.3.1 晶格繞射平面原理 21
2.3.2 電子繞射譜繞射常數測定 24
2.3.3 HRTEM影像處理優化模擬原理 25
2.4 氧化鎂鋅之摻量計算原理 27
第三章 實驗架構與量測儀器 29
3.1 實驗流程與架構 29
3.1.1 實驗流程 29
3.1.2 實驗細部與架構 30
3.1.3 TEM試片之製作方法 33
3.2 掃描式電子顯微鏡 (SEM) 35
3.3 能量散佈光譜儀 (EDS) 37
3.4 高解析穿透式電子顯微鏡 (HR-TEM) 38
3.4.1 穿透式電子顯微鏡的基本原理 38
3.4.2 穿透式電子顯微鏡的結構 39
3.5 X光繞射分析儀 (XRD) 42
3.5.1 X光射線譜 42
3.5.2 分析儀簡介 44
3.6 光激螢光光譜 (PL) 46
3.6.1 光激發螢光原理 46
3.6.2 光激發螢光量測系統架構 48
3.7 拉曼散射光譜 (Raman scattering spectroscopy) 49
3.7.1 拉曼光譜產生的機制與基本原理 49
第四章 實驗結果與討論 52
4.1 製作高方向性且高均度之準直氧化鋅奈米柱 52
4.1.1 氧化鋅緩衝層(ZnO buffer layer)製作參數 52
4.1.2 準直氧化鋅奈米柱成長 55
4.1.3 準直氧化鋅奈米柱SEM與形貌分析 56
4.1.4 準直氧化鋅奈米柱PL分析 60
4.1.5 準直氧化鋅奈米柱XRD分析 61
4.2 以PLD製備氧化鎂鋅包覆準直氧化鋅奈米柱結構 62
4.2.1 氧化鎂鋅包覆層之參數 62
4.2.2 以氧化鎂鋅包覆之形貌分析 63
4.2.3 以氧化鎂鋅包覆之PL分析 81
4.2.4 鎂掺量x之計算 89
4.2.5 以氧化鎂鋅包覆之Raman分析 91
第五章 92
參考文獻 94

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