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博碩士論文 etd-0019116-075034 詳細資訊
Title page for etd-0019116-075034
論文名稱
Title
以化學汽相沉積法生長氧化鋅奈米材料在(0001)/ (1-102) 藍寶石基板
Epitaxial Growth of Zinc Oxide Nanomaterials on (0001)/(1-102) Sapphire Substrate by Chemical Vapor Deposition
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
74
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2015-11-19
繳交日期
Date of Submission
2016-01-26
關鍵字
Keywords
藍寶石、氧化鋅、汽-液-固三相生長機制、化學汽相沉積法
Chemical Vapor Deposition, Sapphire, Zinc Oxide, Vapor-Liquid-Solid method
統計
Statistics
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The thesis/dissertation has been browsed 5671 times, has been downloaded 648 times.
中文摘要
本研究使用化學汽相沉積法 (Chemical Vapor Deposition,CVD)於藍寶石(sapphire)基板,生長氧化鋅實驗中我們首先鍍上一層奈米尺寸的金膜當成催化劑之後利用VLS(Vapor-Liquid-Solid)機制。使用95%氬氣與5%氧氣之混合氣做為反應氣體,以特定比例氧化鋅及碳粉均勻混合後作為反應源前驅物。實驗中同時放入相同處理過程的(0001)與(1-102)面並對不同生長溫度的氧化鋅奈米結構做比較。
以掃描式電子顯微鏡(SEM) 、 X光繞射儀(XRD)分析及探討其表面形貌、晶體結構與生長機制,並使用光致螢光光譜分析(PL)、陰極螢光光譜分析(CL)分析其發光能力與材料缺陷、拉曼光譜分析(Ramam)分析奈米結構之內應力情形,以穿透式電子顯微鏡分析 (TEM)找到各ZnO奈米結構的成長磊晶方向與材料品質分析。經實驗後發現反應溫度在950℃反應時間10分鐘氬氣與氧氣混合氣流量為50 sccm時(0001)藍寶石基板可生長整齊[0002]方向ZnO奈米線,在反應溫度960℃反應時間10分鐘氬氣與氧氣混合氣流量為50 sccm時(11 ̅02)藍寶石基板可獲得整齊且發光性質良好的ZnO奈米梳。
Abstract
In this research, ZnO nano-material grows on sapphire substrate by chemical vapor deposition and Vapor-Liquid-Solid (VLS) growth mechanism. Argon and oxygen are used as carrier gas and reaction gas respectively. Mixed powder of ZnO and graphite are used as reaction sources. Catalyst(Sapphire substrates) is coated by Au. After the reaction, we use scanning electron microscope, x-ray diffractometer, transmission electron microscope, photoluminescence spectroscope, cathodoluminescent and Raman spectroscope to analyze the characteristics of ZnO nano-materials.
In the experiment, Under certain condition (reaction temperature is 950℃; reaction time is 10 minutes ; mixed gas flow of argon and oxygen is 50 sccm), I found that (0001)Sapphire grows uniformly and regularly in the direction of [0002]. Under the condition (reaction temperature is 960℃; reaction time is 10 minutes ; mixed gas flow of argon and oxygen is 50 sccm), I found well-emitted nano combs of ZnO on the (11 ̅02)Sapphire.
目次 Table of Contents
目錄
論文審定書........................................................................................................................i
致謝...................................................................................................................................ii
摘要..................................................................................................................................iii
Abstract...........................................................................................................................iv
目錄...................................................................................................................................v
圖目錄..............................................................................................................................vi
表目錄..............................................................................................................................ix
序論................................................................................................................1
文獻回顧與理論基礎....................................................................................3
2-1 氧化鋅的結構與性質...........................................................................................3
2-2藍寶石基板結構與性質........................................................................................6
2-3化學汽相沉積法....................................................................................................7
2-4 Vapor-Liquid-Solid 成長機制.............................................................................10
實驗內容......................................................................................................12
3-1實驗流程...............................................................................................................12
3-2實驗裝置...............................................................................................................12
3-3實驗步驟...............................................................................................................14
3-4分析與量測系統介紹...........................................................................................16
第四章 實驗結果與討論.............................................................................................18
4-1生長環境對氧化鋅奈米材料之影響...................................................................18
4-1-1 (11 ̅02)藍寶石基板微觀形貌觀察............................................................19
4-1-2 (0001)藍寶石基板為觀形貌觀察..............................................................24
4-1-3 (11 ̅02)結構方向分析..................................................................................29
4-1-4 (11 ̅02)結構方向分析..................................................................................31
4-2增加金膜厚度...........................................................................................................33
4-2-1 (11 ̅02)藍寶石基板為觀形貌觀察.............................................................33
4-2-2 (0001)藍寶石基板為觀形貌觀察.................................................................36
4-3改變反應源的配比...................................................................................................38
4-3-1 (11 ̅02)藍寶石基板為觀形貌觀察...............................................................39
4-4穿透式電子顯微鏡分析 (TEM) .............................................................................42
4-4-1 氧化鋅奈米梳穿透式電子顯微鏡分析.......................................................42
4-4-2 氧化鋅奈米線穿透式電子顯微鏡分析......................................................44
4-5 光致螢光光譜分析(PL) .........................................................................................48
4-5 -1氧化鋅奈米梳光致螢光光譜分析(PL) .....................................................48
4-5 -2氧化鋅奈米線光致螢光光譜分析(PL)......................................................50
4-7陰極螢光光譜分析(CL) ..........................................................................................51
4-7-1氧化鋅奈米梳陰極螢光光譜分析(CL) .......................................................51
4-7-2氧化鋅奈米線陰極螢光光譜分析(CL) .......................................................54
第五章 結論.................................................................................................................57
第六章 參考文獻.........................................................................................................58
附錄拉曼光譜分析(Ramam) ........................................................................................61
圖目錄
圖2-1 圖2-1 氧化鋅三種結構比較示意圖.................................................................3
圖2-2 氧化鋅結晶面.............. ......................................................................................4
圖2-3 藍寶石結構示意圖.............................................................................................6
圖2-4 CVD磊晶機制示意圖.......................................................................................8
圖2-5 CVD中生長條件改變時,邊界層的厚度變化示意圖..................................9
圖2-6 Zn-Au合金相圖...............................................................................................11
圖3-1 實驗流程圖.......................................................................................................12
圖3-2 CVD實驗配置圖.............................................................................................13
圖3-3 鍍金時間與厚度對照圖...................................................................................14
圖3-4 實驗溫度變化曲線圖.......................................................................................15
圖4-1 試片R1在920℃生長SEM影像...................................................................20
圖4-2 試片R2在930℃生長SEM影像...................................................................20
圖4-3 試片R3在940℃生長SEM影像...................................................................21
圖4-4 試片R4在950℃生長SEM影.......................................................................21
圖4-5 試片R5在960℃生長SEM影像...................................................................22
圖4-5-1 試片R5在960℃生長Tile=45∘SEM影像...............................................22
圖4-6 試片R6在970℃生長SEM影像...................................................................23
圖4-7 試片R7在980℃生長SEM影像...................................................................23
圖4-8 試片C1在920℃生長SEM影像...................................................................24
圖4-9 試片C2在930℃生長SEM影像...................................................................25
圖4-10 試片C3在940℃生長SEM影像...................................................................25
圖4-10-1 試片C3在964℃生長Tile=45∘SEM影像............................................26
圖4-11 c-plane試片C4在950℃生長SEM影像....................................................26
圖4-12 試片C5在960℃生長SEM影像.................................................................27
圖4-13 在r-plane上生長氧化鋅奈米結構反應溫度...............................................30
圖4-14 在c-plane上生長氧化鋅奈米結構反應溫度...............................................32
圖4-15 試片R8在940℃生長SEM影像.................................................................34
圖4-16 試片R9在950℃生長SEM影像.................................................................34
圖4-17 試片R910在970℃生長SEM影像.............................................................35
圖4-18 試片R11在980℃生長SEM影像...............................................................35
圖4-19 試片C7在940℃生長SEM影像.................................................................36
圖4-20 試片C6在950℃生長SEM影像.................................................................37
圖4-21 試片C8在960℃生長SEM影像.................................................................37
圖4-22 試片C9在970℃生長SEM影像.................................................................38
圖4-23試片R12在960℃生長SEM影像..................................................................40
圖4-24 試片R13在970℃生長SEM影像...............................................................40
圖4-25 試片R14在970℃生長SEM影像...............................................................41
圖4-26 R5試片氧化鋅奈米梳 TEM影像圖 zone axis為[-1-120] ......................43
圖4-27 R5試片氧化鋅奈米梳選區電子繞射圖zone axis為[-1-120] ..................43
圖4-28 (a)試片C3截面穿透式電子顯微鏡影像 (b)氧化鋅奈米線之根部
選區電子繞射圖 (c) (0001)氧化鋁基板之選區電子繞射圖......................................45
圖4-29 氧化鋅奈米線TEM明視野影像 成相條件g=0002…….........................46
圖4-30 氧化鋅奈米線TEM暗視野影像 成相條件g=0002.................................46
圖4-31 氧化鋅奈米線TEM影像擷取金點位置 ....................................................47
圖4-32 試片C3 對氧化鋅底部進行EDS 元素成分分析.....................................47
圖4-33 試片R1(920℃)、R2(930℃)、R3(940℃)之PL光譜...............................49
圖4-34 試片R4(950℃)、R5(960℃)、R6(970℃)之PL光譜................................49
圖4-35 試片C3(940℃)、C4(950℃)、C5(960℃)之PL光譜................................50
圖4-36 試片R5之(a) CL光譜分析(b)SEM影像圖(c)CL影像對照圖.................52
圖4-37 試片R6之(a) CL光譜分析(b) SEM影像圖 (c)CL影像對照圖..............53
圖4-38 試片C3之(a) CL光譜分析(b) SEM影像圖(c)CL影像對照圖................55
圖4-39 試片C4之(a) CL光譜分析(b) SEM影像圖(c)CL影像對照圖................56
圖A-40 (11 ̅02)氧化鋁基板之Raman光譜圖..........................................................61
圖A-41 試片R5之Raman光譜圖.............................................................................62
圖A-42 試片R6之Raman光譜圖.............................................................................62
圖A-43 試片(0001)氧化鋁基板之Raman光譜分析圖.............................................63
圖A-44 試片C3之Raman光譜圖.............................................................................64
圖A-45 試片C4之Raman光譜圖............................................................................65

表目錄
表2-1 氧化鋅性質.......................................................................................................5
表2-2 藍寶石基本資料...............................................................................................6
表2-3 碳與氧化鋅發生碳熱還原反應之反應及其自由能.....................................11
表2-4 缺乏氧氣環境下碳與氧化鋅發生碳熱還原之三項反應式.........................11
表4-1 改變反應溫度之實驗參數表……….............................................................18
表4-2 藍寶石的JCPDS card.......................................................................................28
表4-3 氧化鋅的JCPDS card.......................................................................................28
表4-4 改變鍍金秒數之實驗參數...............................................................................33
表4-5 改變反應溫度之實驗參數...............................................................................38
表4-6 改變反應源比例之實驗參數...........................................................................39
表4-7 試片C3 對氧化鋅底部進行EDS 元素成分分析含量結果........................47
參考文獻 References
第六章 參考文獻
1. P.Zu, Z.K.Tang, G. K. L. Wang, M. Kawasaki, A. Ohtomo, H. Koinuma, and Y. Segawa, Solid State Commun, 103 (1997) 459.
2. D.C. Look, Mater Sci Eng, B80 (2001) 383.
3. I. Akasaki, H. Amano, Y. Koide, K. Hiramatsu, and N. Sawaki, J. Cryst. Growth, 98 (1989) 209.
4. J .X. Wang, X. W .Sun, Y. Yang, H.Huang , Y.C.Lee, O.K.Tan,L.Vayssieres, Nanotechnology,17 (2006) 4995.
5. Q. Wan, Q. H. Li, Y. J. Chen, T. H. Wang, X. L. He, J. P. Li, C. L. LinAppl. Phys. Lett.84(2004)3654
6. S.M. Lukas,L.M.D. Judith, Mater Today,10 (2007) 40.
7. J. S. Park, S. K. Homg, and T. Minegishi, Appl. Sur. Sci, 254 (2008) 7786.
8. P. Fons, K. Iwata, A. Yamada, K. Matsubara, S. Niki, K. Nakahara, T. Tanabe and H. Takasu, Appl. Phys. Lett. 77 (2000) 1801.
9. Z.C. Feng, in: Handbook of Zinc Oxide and Related Materials: Volume One, Materials, CRC Press, September (2012).
10. X. Tang, F. Hossain, K. Wongchotigul, M. G. Spencer, Appl.Phys. Lett.,72 (1998). 1501
11. W. L. Chen, R. L. Gunsh, Jung Han, K. Higashimine, N. Otsuka, MRS Intenet J. Nitride Semicond. Res.5S1,W3 (2000) 30
12. Ü. Özgür, Ya.I. Alivov, C. Liu, A. Teke, M.A. Resschikov, S. Doğan, V. Avrutin, S.J. Cho, and H. Morkoc, J. Appl. Phys., 98 (2005) 041301.
13. D. P. Norton, Y. W. Heo, M. P. Ivill, K. Ip, S. J. Pearton, M. F. Chisholm, and T. Steiner, Materials Today, 7 (2004) 34.
14. X. T. Zhang, Y. C. Liu, Z. Z. Zhi, J. Y. Zhang, Y. M. Lu, D. Z. Shen, W. Xu, X. W. Fan, X. G. Kong, J. Lumin., 99 (2002) 149.
15. A. Janotti and C.G. Van de Walle, Appl. Phys. Lett,87 (2005) 122102
16. T. M.Børseth, B. G. Svensson, A. Yu. Kuznetsov, P. Klason, Q. X. Zhao, and M. Willander, Appl. Phys. Lett,89 (2006) 262112
17. F. Claeyssens, C.L. Freeman, N.L. Allan, Y. Sun, M.N.R. Ashfold, J.H. Harding, J. Mater. Chem., 15 (2005) 139.
18. K. Maeda, M. Sato, I. Niikura T. Fukuda, Semicond. Sci. Technol. S49 (2005) 20
19. D.K.Hwang, H.S.Kim, J.H.Lim, J.Y. Oh, J.H. Yang, S.J.Park, K.K. Kim, D. C. Look, Y. S. Park, Appl. Phys. Lett,86 (2005) 151917
20. Z.W. Wang, Y.Yue, Y.Cao, VACUUM,101 (2014) 313
21. J.C. Fan,C.C. Ling ,Z.Xie, Optoelectronics - Materials and Techniques, 16 (2011) 394.
22. D. P. Norton, Y. W. Heo, M.P. Ivill, K. Ip, S.J. Pearton, M.F. Chisholm, and T. Steiner, Mater. Today, 7 (2004) 34.
23. 江建德,”以氫化物氣相磊晶法在藍寶石及圖案畫藍寶石基板生長氮化镓厚膜”國立中山大學材料與光電科學研究所碩士論文(2013).
24. H.O.Pierson,“Handbook of Chemical Vapor Deposition”,Second Edition,(1999) 12
25. R.S. Wagner and W.C. Ellis, Appl. Phys. Lett., 4 (1964) 89.
26. R. Thapa, B. Saha, K.K. Chattopadhyay, J ALLOY COMPD, 475 (2009) 373.
27. X.C. Wu*, Y.R. Tao, J CRYST GROWTH, 242 (2002) 309.
28. B.Wang, Y.H.Yang ,G.W.Yang,nanotechnology, 17 (2006) 4682.
29. V. Gottschalch , G. Wagner , J. Bauer , H. Paetzelt , M. Shirnow, J CRYST GROWTH,310 (2008) 5123.
30. T. Ogino ,, M. Yamauchi, Y. Yamamoto, K. Shimomura n , T. Waho, J CRYST GROWTH, 414 (2015) 161.
31. T.Grap,T.Rieger,C.Blomers,T,Schapers,D.Grutzmacher ,M.I.Lepsa,Nanotechnology,24 (2013) 335601.
32. T.Xu, P.Ji,M.He,J.Li, J Nanomater, (2012) 797935.
33. S. Huang, Q. Cai, J. Chen, Y. Qian, L. Zhang, J. Am. Chem. Soc., 131 (2009) 2094.
34. M. H. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E. Weber, R. Russo, P. Yang, Science, 292 (2001) 1897.
35. M.H. Huang, Y. Wu, H. Feick, N. Tran, E. Weber, and P. Yang, Advanced Materials, 13 (2001) 113.
36. Y. K. Rao, “Stoichiometry and Thermodynamics of Matallurgical Processes”, Cambridge University Press, New York (1985).
37. MTDATA-Phase Diagram Software from the National Physical Laboratory
38. 蘭彥廷”以化學氣相沉積法在(100)鋁酸理基板上成長氧化鋅奈米材料”國立中山大學材料與光電科學研究所碩士論文 (2012)
39. Z. W. Pan, Z. R. Dai, Z. L. Wang, Science, 291 (2001) 1947.
40. 24PCPDFWIN,ver.1.30(JCPDS-I nternational Center for Diffraction Data,1997).
41. R.S. Wagner, W.C. Ellis, Appl. Phys. Lett, 4 (1964) 89.
42. A.Aminzadeh,H.Sarikhani-fard,Spectochim.Acta A55, (1999) 1421.
43. N. Ashkenov et al., J. Appl. Phys, 93 (2003) 126.
44. J. F. Scott, Phys. Rev. B 2, (1970) 1209.
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