臺灣博碩士論文加值系統

「自供電技術」是一種能夠不依靠任何外部電源，即可自行持續運作的系統，其主要應用於結合各種感測器、數據處理及傳輸等。
第一部分是材料分析，主要以改變鎵摻雜濃度，來探討其結構變化及特性的穩定性。透過「射頻磁控濺鍍機」在ITO玻璃基板上，濺鍍100nm氧化鋅薄膜，作為晶種層。接著利用水熱法配置硝酸鋅、四氮六甲圜(HMTA)，以及不同濃度之硝酸鎵，生長鎵摻雜氧化鋅奈米結構。將試片透過-場發射掃描式電子顯微鏡(FE-SEM)、能量散佈分析儀(EDS)、穿透式電子顯微鏡(TEM)、X光繞射頻譜圖分析(XRD)及螢光光譜儀(PL)，進行生長結構、材料成分、晶格缺陷、結晶度等分析。
第二部分是元件組成與分析，主要是先以雷射雕刻定義圖形，再透過濺鍍法於PET基板上沉積銀薄膜備製電極，然後與鎵摻雜氧化鋅奈米柱組裝成奈米發電機，利用敲擊系統驅動其奈米發電機使奈米柱彎曲及機械能轉換成電能的機制，並分析量測出照UV光前與照UV光後的壓電電壓。

Self-Powered Technology is a system that can operate continuously without any external power supply. It is most applied in integrate with sensors for data processing and transmission, etc.
Part 1 Material Analysis：
In this study, the point is to change the doping concentration of Gallium, to explore the stability of its structure and characteristics. A 100nm Zinc Oxide film was sputtered on the ITO glass substrate by a "RF Magnetron Sputtering Machine" as a seed crystal layer. Then, Zinc Nitrate, Hexamethylene Tetrazole (HMTA), and Gallium Nitrate with different concentrations are prepared by Hydrothermal method to grow Gallium-doped Zinc Oxide nanostructures. The test piece was analyzed by Transmission-Field Emission Scanning Electron Microscope (FE-SEM), Energy Dispersive Analyzer (EDS), Transmission Electron Microscope (TEM), X-ray Diffraction Spectrum Analysis (XRD) and Fluorescence Spectrometer (PL).) to analyze the growth structure, material composition, lattice defects, crystallinity, etc.
Part 2 Composition and Analysis：
In this study, the pattern is defined by laser engraving. The electrode is prepared by depositing silver film on PET substrate by sputtering method, and then it is assembled with Gallium-doped Zinc Oxide nanopillars to form a nanogenerator, and the mechanism of driving its nano generator by knocking system to bend the nano column and convert mechanical energy into electrical energy. The percussion system drives its nanogenerators and measures the piezoelectric voltage before and after UV illumination.

摘要......................................................................i
Abstract.............................. ii
誌謝..............................iii
目錄..............................iv
表目錄..............................vi
圖目錄..............................vii
第一章 緒論.............................. 1
1.1 前言 ................................................................................................................................. 1
1.2 研究動機與目的 ............................................................................................................. 2
第二章 基礎概念.............................. 3
2.1 氧化鋅的基本特性 ......................................................................................................... 3
2.1.1 氧化鋅不同型態的結構 ....................................................................................................... 4
2.1.2 氧化鋅之發光機制 ............................................................................................................... 4
2.2 濺鍍原理 ......................................................................................................................... 6
2.2.1 射頻磁控濺鍍原理 ............................................................................................................... 6
2.3水熱法成長奈米結構 ...................................................................................................... 9
2.4 成長氧化鋅奈米柱的反應流程 ................................................................................... 11
2-5 成長鎵摻雜氧化鋅奈米柱陣列之化學反應流程 ....................................................... 12
2.6 壓電效應原理 ............................................................................................................... 12
2.6.1 壓電效應的介紹 ................................................................................................................. 13
2.6.2 壓電效應的解釋 ................................................................................................................. 15
2.6.1 正壓電效應的解釋 ............................................................................................................. 15
2.7 精密敲擊系統 ............................................................................................................... 16
2.7.1 精密敲擊系統原理 ............................................................................................................. 16
2.7.2 精密敲擊系統的優點 ......................................................................................................... 16
2.8光響應度(Responsivity) ................................................................................................. 18
2.9內部增益( Internal gain ) ............................................................................................... 18
2.10紫外光照射氧化鋅時能帶圖解釋 .............................................................................. 19
2.10紫外光照光前後的氧化鋅流程與解釋 ...................................................................... 21
第三章
實驗步驟及機台介紹 ...................22
3.1 實驗機台與藥品 ........................................................................................................... 22
3.2 實驗架構 ....................................................................................................................... 24
3.3 生長鎵摻雜氧化鋅奈米柱陣列 ................................................................................... 26
3.3.1 基板的準備 ......................................................................................................................... 26
3.4 電極製作 ....................................................................................................................... 26
3.4.1 上電極的製作 ..................................................................................................................... 27
3.4.2下電極之製作 ...................................................................................................................... 28
3.5 材料特性之分析 ........................................................................................................... 28
3.5.1 .場發射掃描式電子顯微鏡（Field-Emission Scanning Electron Microscope,FE-SEM） ...................28
3.5.2 能量散射光譜儀(Energy Dispersive Spectrometry, EDS)................... 29
3.5.3 穿透式電子顯微鏡(Transmission Electron Microscope,TEM)
......................................... 29
3.5.4 X光繞射分析儀（X-Ray Diffraction, XRD） .................................................................. 30
3.5.5 光激發螢光光譜儀(PL) ..................................................................................... 30
第四章 實驗內容與討論 ...................33
4.1 鎵摻雜氧化鋅奈米柱備制 ........................................................................................... 33
4.2鎵摻雜氧化鋅奈米柱之表面型態分析 ........................................................................ 34
4.3鎵摻雜氧化鋅奈米柱之穿透式電子顯微鏡分析 ........................................................ 39
4.4鎵摻雜氧化鋅奈米柱之X光能譜散佈分析 ............................................................... 42
4.5鎵摻雜氧化鋅奈米柱之X光繞射分析 ....................................................................... 44
4.6鎵摻雜氧化鋅奈米柱之光激發螢光光譜分析 ............................................................ 45
4.7鎵摻雜氧化鋅奈米柱之自發電元件特性分析 ............................................................ 47
第五章 結論................... 55
5.1結論 ................................................................................................................................ 58
5.2未來展望 ........................................................................................................................ 58
參考文獻...................59
Extended Abstract................... 59
Abstract ...................................................59

[1] L. Vayssieres, “Growth of Arrayed Nanorods and Nanowires of ZnO from Aqueous Solutions” Adv. Mater., vol. 15, no. 5, pp. 464-466, 2003. [2] L. Vayssieres, K. Keis, A. Hagfeldt, and S. E. Lindquist, Chem., “Three-Dimensional Array of Highly Oriented Crystalline ZnO Microtubes” Mater. vol. 13, no. 12, pp.4395-4398, 2001. [3] L. Vayssieres, K. Keis, S. E. Lindquist, and A. Hagfeldt, “Purpose-Built Anisotropic [4] MetalOxide Material: 3D Highly Oriented Microrod Array of ZnO” J. Phys.Chem.B, vol. 105, no. 17, pp.3350-3352, 2001. [5] Q. Li, V. Kumar, Y. Li, H. Zhang, T. J. Marks, and R. P. H. Chang, “Fabrication of ZnO Nanorods and Nanotubes in Aqueous Solutions” Chem. Mater. vol. 17, no. 5, pp. 1001-1006, 2005.
[6] L. E. Greene, M. Law, J. Goldberger, F. Kim, J. C. Johnson, Y. Zhang, R. J. Saykally, and P. D.Yang, “Low-Temperature Wafer-Scale Production of ZnO Nanowire Arrays” Angew. Chem.Int. vol. 42, no. 26, pp. 3031-3034, 2003.
[7] K. Govender, D. S. Boyle, P. B. Kenway and P. O’Brien, “Understanding the factors thatgovern the deposition and morphology of thin films of ZnO from aqueous solution” J. Mater. Chem., vol. 14, pp. 2575-2591, 2004.
[8] J. Lin,P. Fei,J. Song,X. Wang,C. Lao,R. Tumala,and Z. L. Wang, “Carrier density and schottky barrier on the performance of DC nanogenerator” Nano Lett. vol. 8, no. 1, pp. 328-332, 2008.
[9] Z. L. Wang,X. D. Wang,J. Song,J. Liu,and Y. F. Gao, “Piezoelectric nanogenerators for self-powered nanodevices” IEEE Perv.Comp. vol. 7, no. 49, pp.135-172, 2008.
[10] Q.Yingyu,W. Zhenping and A. Meilin.2016.“EnhancedGa2O3/SiCultraviolet photodetector with graphene top electrodes,” JOURNAL OF ALLOYS AND COMPOUNDS , 680. 247-251.
[11] Y. Ji, T. Ning and D. Y. Fu. 2016. “Ultraviolet photodetector based on sol-gel synthesized MgZnO nanoparticle with photoconductive gain,”JOURNAL OF ALLOYS AND COMPOUNDS , 667. 359-362.
[12] M. Xu, Q. Li, Y. Ma and H. Fan. 2014. “Ni-doped ZnO nanorods gas sensor: Enhanced gas-sensing properties, AC and DC electrical behaviors,” Sensors and Actuators B ,199. 403-409.
[13] C.Shao, Y. Chang and Y. Long. 2014. “High performance of nanostructured ZnO film gas sensor at roomtemperature,” Sensors and Actuators B , 204. 666-672.
[14] Y. Jing L. Dong and Z. Lixin. 2016. “Application of ZnTiO3 in quantum-dot-sensitized solar cells and numericalsimulations using first-principles theory,” JOURNAL OF ALLOYS AND COMPOUNDS , 681. 88-95.
60
[15] W. Lei , M. Cheng and H. Ke. 2016. “Two-stage co-evaporated CuSbS2 thin films for solar cells,” JOURNAL OF ALLOYS AND COMPOUNDS , 680. 182-190.
[16] C.L. Hsu, C.W. Sua and T.J. Hsueh, 2014. “Enhanced field emission of Al-doped ZnO nanowires grown on a flexible polyimide substrate with UV exposure,” RSC Advances, 4,2980-2983.
[17] S.J. Young , Member, IEEE, and Y.H. Liu. 2015. “Enhanced Field Emission Properties of Two-Dimensional ZnO Nanosheets Under UV illumination,” IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS , 21(4). JULY/AUGUST 2015.
[18] W. C. Liang , L. C. Yi and C. Yun. 2016. “Fabrication of efficient polymer light-emitting diodes using water/alcohol soluble poly(vinyl alcohol) doped with alkali metal salts as electron-injection layer,” JOURNAL OF MATERIALS SCIENCE , 51(15).7286-7299.
[19] J. Jayaraman , P. Annadurai and T. Venugopal. 2016. “Hybrid organic-inorganic light emitting diodes: Effect of Ag-doped ZnO,” JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY , 325. 88-96. [20] S. H. Seoa, W.C. Shinb, J. S. Parkb,“A novel method of fabricating ZnO/diamond/Si multilayers for surfaceacousticwave (SAW) device applications”, Thin Solid Films Volume 416 ,Pages 190–196(2002) [21] S. A. Studenikin, N. Golego, and M. Cociver “Fabrication of green and orange photoluminescent, undoped ZnO films using spray pyrolysis” J, Appl. Phys, Vol. 84(1998) [22] T. M. Barnes, J. Leaf, S. Hand, C. Fry and C. A. Wolden, “A comparison of plasma-activated N2/O2 and N2O/O2 mixtures for use in ZnO:N synthesis by chemical vapor deposition,” J, Appl. Phys., vol. 96, pp. 7036-7044, (2003) [23] H.S. Randhawa, M.D. Matthews and R.F. Bunshan, "SnO2 Films Prepared by Activated Reactive Evaporation”, Thin Solid Films, 83, 267-271, (1981). [24] F. Furusaki, J. Takahashi and K. Kodaira,"Preparation of ITO Thin Films by Sol-Gel Method”, J. of the Japan Ceramic Society, Vol.102, pp.200-205, (1994). [25] E. S Shim et al., “Effect of The Variation of Films Thickness on The Structural and Optical Properties of ZnO Thin Films Deposition on Sapphire Substrate Using PLD”, Appl. Surf. Sci. ,186, 474-476, (2002). [26] Yasuhiro Igasaki and Hiromi Saito, “The Effects of Zinc Diffusion on The Electrical and Optical Properties of ZnO: Al Films Prepared by RF Reactive Sputtering ”, Thin Solid Films, 199, pp. 223-230 ,(1991).
[27] J. J. Wu, S. C. Liu, C. T. Wu, K. H. Chen and L. C. Chen, Appl. Phys. Lett.,2002 81, 1312. [28] H.E. Unalan, P. Hiralal, N. Rupesinghe, S. Dalal, W.I. Milne, G.A.J. ,2008, “Amaratunga,Rapid synthesis of aligned zinc oxide nanowires”.
61
[29] C.H. Lu, Y.C. Lai, R.B. Kale,2009, “Influence of alkaline sources on the structural and morphological properties of hydrothermally derived zinc oxide powders” Alloys Compd. 477 (1-2) 523-528.
[30] X. Y. Kong, Y. Ding and Z. L. Wang, J. Phys. Chem. B, 2004, 108, 570.
[31] P. D. Yang, H. Q. Yan, S. Mao, R. Russo, J. Johnson, R. Saykally, N. Morris, J.Pham, R. He and H. J. Choi, Adv. Funct. Mater.2002.
[32] L. Vayssieres, Adv. Mater., 2003, 15, 464. [33] T.M. Shang, J.H. Sun, Q.F. Zhou, M.Y. Guan,2007 “ Controlled synthesis of various morphologies of nanostructured zinc oxide: flower, nanoplate, and urchin, Cryst. ” Res. Technol. 42 (10) 1002-1006.
[34] 趙偉迪。趙偉迪。2009。氧化鋅奈米線應用於發光二極體之研製。碩士論文。國立台灣師範。氧化鋅奈米線應用於發光二極體之研製。碩士論文。國立台灣師範大學大學機電科技研究所。機電科技研究所。
[35] 高義典。高義典。2013。以。以 Hotwire 系統輔助系統輔助 LPCVD 法製程鈦法製程鈦/銅摻雜氧化鋅奈米柱之研究。銅摻雜氧化鋅奈米柱之研究。碩碩士論文。國立臺南士論文。國立臺南大學大學電機工程研究所。電機工程研究所。
[36] K. Vanheusden , W. L. Warren, C. H. Seager, D. R. Tallant and J. A. Voigt. 1996. “Mechanisms behind green photoluminescence in ZnO phosphor powders”, Journal of Applied Physics.
[37] B. Lin and Z. Fu. 2001. “Green luminescent center in undoped zinc oxide films deposited on silicon substrates”, Applied Physics Letters
[38] 林筱玫，2011，TiO2/Ag/TiO2複何多層膜特性分析與旗光檢測器元件之應用，國立虎尾科技大學光電與材料科技研究所
[39] F. Shinoki and A. Itoh, 1975, “Mechanism of rf reactive sputtering”, Journal of Applied Physics., p. 3381-3384.
[40] 吳誠智，2012，氧化鋅光電元件特性之研究，國立虎尾科技大學光電與材料科技研究所 [41] ]Hongfang Li, Xiaohua Zhang, Yunqing Zhu, Ru Li,Hongyuan Chen, Peng Gao,Yongyi Zhang,Taotao Li,Yongning Liuc and Qingwen Li,2014 , “Hydrothermal deposition of a zinc oxide nanorod array on a carbon nanotube film as a piezoelectric generator”.
[42] 吳朗, 電子陶瓷-壓電, 台北市, 全欣科技圖書,民83, pp7-13
[43] 楊信興，2009，磊晶成長氧化鋅奈米結構應用於可撓性壓電式奈米發電機系統，國立虎尾科技大學光電與材料科技研究所
[44] K. Nakajima, T. Iida, K. I. Sugimoto, H. Kan, and Y. Mizushima, “Properties and design theory of ultrafast GaAs metal-semiconductor-metal photodetector with symmetrical Schottky contacts”, IEEE Transaction on. Electron Devices, vol. 37, pp. 31-35 (1990).
[45] C. Carrano, T. Li, P. A. Grudowski, C. J. Eiting, R. D. Dupuis, and J. C. Campbell, “High quantum efficiency metal-semiconductor-metal ultraviolet photodetectors fabricated on single-crystal GaN epitaxial layers”, Electron. Lett, vol. 33, pp. 1980-1981 (1997).Katz, V. Garber, B. Meyler, G. Bahir,and J. Salzman, “Gain mechanism in [45]GaN Schottky ultraviolet detectors”, Appl. Phys. Lett., vol. 79, pp. 1417 (2001).
62
[46] J. C. Carrano, T. Li, P. A. Grudowski, C. J. Eiting, R. D. Dupuis, and J. C. Campbell, “Comprehensive characterization of metal–semiconductor–metal ultraviolet photodetectors fabricated on single-crystal GaN”, J. Appl. Phys., vol. 83, pp. 6148-6160 (1998) [47] K. Govender, D. S. Boyle, P. B. Kenway, P. O’Brien*, J. Mater. Chem., 2004, 14,2745 “Understanding the factors that govern the deposition and morphology of thin films of ZnO from aqueous solution” [48] Y. Purusothaman, N. R. Alluri, A. Chandrasekhar and S. KIM, J. Mater. Chem. C, 2016 “Elucidation of Unsymmetrical Effect on the Piezoelectric and Semiconducting Properties of Cd doped 1D-ZnO Nanorods” [49] Weiwei Wu, Suo Bai, Miaomiao Yuan, Yong Qin,* Zhong Lin Wang,* and Tao Jing, VOL. 6 ’ NO. 7 ’ 6231–6235 ’ 2012” Lead Zirconate Titanate Nanowire Textile Nanogenerator for Wearable Energy-Harvesting and Self-Powered Devices” [50] Mingli Zheng , Feng Yang , Junmeng Guo , Lei Zhao , Xiaohong Jiang , Guangqin Gu , Bao Zhang , Peng Cui , Gang Cheng *, Zuliang Du “ Cd(OH)2@ZnO nanowires thin-film transistor and UV photodetector with a floating ionic gate tuned by a triboelectric nanogenerator” [51] Feng Yang, Junmeng Guo, Lei Zhao, Wanyu Shang, Yanyuan Gao, Song Zhang ,Guangqin Gu , Bao Zhang , Peng Cui , Gang Cheng, , Zuliang Du “Tuning oxygen vacancies and improving UV sensing of ZnO nanowire by micro-plasma powered by a triboelectric nanogenerator”
[52] Majid Taghavi,Virgilio Mattoli ,Barbara Mazzolai,Carlo Filippeschi and Lucia Beccai “Synthesizing tubular and trapezoidal shaped ZnO nanowires by an aqueous solution method”