本研究提出新穎式3D奈米微發電機製作，選擇氧化鋅(ZnO)為壓電材料，使用電噴霧法(Electrospray)噴灑ZnO奈米粒子在金(Au)和鉻(Cr)的矽(Si)基板上，整個研究涵蓋ZnO壓電材料成長及物性分析與發電元件設計。首先使用溶膠-凝膠(Sol-gel)法混合乙醇胺(Ethanolamine)和乙二醇甲醚(2-Methoxyethanol)溶劑溶入醋酸鋅(Zinc Acetate)中形成前驅物溶膠。藉著改變前驅物溶膠參數製備均勻透明的最佳化Sol-gel溶液，提供電噴霧法製作Sol-gel奈米粒子。當針頭前端通以直流電壓時，Sol-gel溶液會因電場與表面張力形成泰勒錐(Taylor cone)噴灑Sol-gel奈米粒子於收集板上，再進行退火處理後形成ZnO奈米粒子。實驗中探討改變Sol-gel溶液參數、驅動電壓、電噴霧針頭與收集板的距離、X-Y軸平台移動次數和退火溫度找出較佳參數。製備ZnO奈米柱方面，利用較佳結晶特性的ZnO奈米粒子作為晶種層，搭配水溶液法固定溫度90℃，探討改變硝酸鋅(Zinc nitrate)和六亞甲基四胺(HMTA)莫爾濃度比與成長時間，製備高深寬比ZnO奈米柱。物性分析方面，ZnO奈米柱壓電特性和晶體表面結構利用X光射線繞射儀(X-ray diffraction, XRD)和場發射掃描式電子顯微鏡(Field emission scanning electron microscopy, FESEM)更近一步探討。XRD證明ZnO奈米粒子隨著退火溫度增加和ZnO奈米柱高度越高，具有良好的C 軸優選取向。ZnO奈米柱表面結構部份由FESEM觀察出隨著成長時間與材料莫爾濃度比變化下，高度會隨著改變。但反應濃度若降低時，奈米柱高度會漸漸的被析出，其ZnO奈米柱直徑約為100 nm-400 nm和高度約為200 nm-1200 nm。並利用X光成份分析系統(EDAX)分析材料成份，証明本實驗的ZnO材料並無其他雜質。最後在電性量測部分，利用半導體材料的蕭特基(Schottky)接觸，濺鍍鉑(Pt)在ZnO奈米柱做為上電極封裝下電極的ZnO奈米柱結構，置放超音波震盪機使Pt壓迫ZnO奈米柱產生相對運動而變形，實驗發現頻率42 kHz下量出最大的輸出功率為0.004х10-8 W。

This study presents a new way for new 3D energy harvesting energy with vertically aligned nanorods arrays. ZnO nanoparticles array on Au/Cr/Si substrate are directly patterned by electrospray. First, gel solutions with zinc acetate, monoethanolamine and 2-methoxyethanol as the precursor by sol-gel technology were formulated. Then, the solutions were stirred to become clear and homogeneous liquid. Second, the precursor solutions were prepared by electrospray, where a Taylor cone was formed to produce ZnO nanoparticles. Then the ZnO nanoparticles were annealed as seed layers for nanorods. By varying the property of the ZnO solution, needle with collector distance, applied voltage, annealing temperature and molar ratio were discussed. After annealing, the orientation of the ZnO nanorods depend on the crystalline orientation of ZnO nanoparticles. The ZnO nanorods were obtained at a temperature of 90 °C by aqueous solution method. The experimental parameters of lengths, diameters, and pH level of the reaction medium of the Zno nanorod were observed and controlled. The physical structures of ZnO were characterized by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) analyses. The results show that the ZnO nanoparticles become more intensity with increasing in annealing temperature. The SEM analysis reveals that the ZnO nanorods have diameters about 100-400 nm and length about 200-1200 nm. Finally, Pt electrode atop as Schottky contacts were packed to fabricate nanogenerator with ZnO nanorods. Then the nanogenerator was driven by ultrasonic wave vibration. The wave drives the electrode up and down to vibrate the nanorods, and its voltage and current were also characterized. The measurement results show the maximum power is 0.004х10-8 W during the operation frequency of 42 kHz.

第一章 序論 1
1.1 前言 1
1.2 研究動機與目的 2
1.3 文獻回顧 2
1.4 本文架構 7
第二章 理論基礎與原理 8
2.1 壓電材料 8
2.1.1 氧化鋅基本結構與應用 9
2.1.2 晶體結構 9
2.2 壓電效應原理 11
2.2.1正壓電效應(機械能轉電能) 11
2.2.2逆壓電效應(電能轉機械能) 12
2.3溶膠-凝膠法 16
2.3.1溶膠-凝膠法製作原理 17
2.3.2溶膠-凝膠法反應步驟 17
2.4電噴霧法製作背景 19
2.4 .1 電噴霧法製作原理 20
2.4 .2 電噴霧參數特性 22
2.5氧化鋅奈米結構之成長機制 24
2.5 .1 陽極氧化鋁法 24
2.5 .2 固-液-氣法 24
2.5 .3 溶液-液-固法 25
2.5 .4 非等向性成長法 25
2.6 水溶液法 26
2.6 .1 水溶液法介紹 26
2.6 .2 水溶液法合成一維氧化鋅成長機制 26
2.7 氧化鋅奈米發電機 28
2.7 .1 蕭特基接觸 28
2.7 .2 壓電式發電機原理 31
第三章 研究方法 32
3.1 實驗架構 32
3.1.1 實驗藥品 33
3.2 前驅物配製 34
3.3 電噴霧製作氧化鋅微奈米粒子方法 35
3.3 .1 電噴霧實驗儀器介紹 35
3.3 .2 濺鍍製程 36
3.3 .3 氧化鋅電噴霧製作流程 36
3.3 .4 電噴霧製程參數操作條件 37
3.4 水溶液法成長氧化鋅奈米柱 39
3.5實驗分析儀器 41
3.5.1 X光粉末繞射儀 41
3.5.2 場發射掃描式電子顯微鏡 42
第四章 實驗結果與討論 43
4.1 X光射線繞射儀分析 43
4.1.1 氧化鋅晶種層 43
4.1.2 氧化鋅奈米柱 48
4.2場發射掃描式電子顯微鏡分析 48
4.2.1有無濺鍍金屬成長氧化鋅差異性 49
4.2.2 不同成長時間與反應濃度 52
4.2.3 能量分散光譜分析 78
4.3 奈米發電機元件設計 80
4.3.1 奈米發電機封裝 80
4.3.2 奈米發電機電性量測 82
第五章 結論與未來展望 87
5.1 結論 87
5.2 未來展望 88
參考文獻 89

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