臺灣博碩士論文加值系統

當材料在奈米尺度時，會有不同於以往的尺寸效應，不論在光性、電性、磁性方面都有別以往的效果產生。鋅是一個重要元素，具有低熔點及沸點的特性。本實驗利用微波電漿輔助化學氣相沉積法成功合成出氧化鋅奈米柱、硫化鋅奈米線、硒化鋅奈米棒，從場發射掃描式電子顯微鏡(FE-SEM)中觀察其表面形貌，再利用高解析穿透式電子顯微鏡(HRTEM)和電子選區繞射(SAD)來確認單晶結構，且定義ZnO成長方向[001]; ZnS成長方向[002]; ZnSe成長方向[111]，另外從X光繞射分析儀(XRD) X光電子能譜儀(XPS) 微拉曼光譜(Raman)對結構成份和化學態做進一步分析。
除此之外，利用光激發光譜(PL)來分析三種鋅化合物的發光波段，ZnO紫外光發光位置為384nm，ZnS紫外光發光波段為338nm，ZnSe藍光發光波段為465nm。

When in nano-scale, materials bear different characteristics, suck as optical, electrical, and magnetic properties. Zinc is an important element with low melting point and boiling point characteristic. In this work, zinc oxide nanocolumn、zinc sulfide nanowires、zinc selenide nanobars have been successfully synthesized by MPECVD(microwave plasma enhanced chemical vapor deposition). Use field emission scanning electron microscope(FESEM) to observe the surface morphology and use high resolution transmission electron microscopy(HRTEM) micrographs and selected area diffraction (SAD) to show the crystalline patterns of zinc compound nanostructures. ZnO growth direction is of [001], ZnS [002] and ZnSe [111].The structure and composition were characterized by means of X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy.
The emission bands of the three zinc compounds were analyzed by photoluminescence (PL). ZnO UV emission is at 384nm, ZnS UV emission is at 338nm, and ZnSe blue emission is at 465nm.

誌謝 I
摘要 III
Abstract IV
目錄 VI
圖目錄 XI
表目錄 XVII
第一章 序論 1
1-1 奈米科技概述 1
1-2 奈米科技的特性 3
1-2.1 小尺寸效應[7] 3
1-2.2 量子尺寸效應[8] 4
1-2.3 量子侷限效應 4
1-2.4 量子穿隧效應[9] 4
1-2-5 量子干涉效應 5
1-3 奈米科技的發展 5
1-4 研究動機 12
第二章 文獻回顧 13
2-1氧化鋅結構與特性 13
2-1.1氧化鋅發光機制 16
2-2硫化鋅結構與特性 18
2-2.1硫化鋅發光機制 20
2-3硒化鋅結構與特性 21
2-3.1硒化鋅發光機制 23
2-4鋅化合物性質比較 26
2-5 鋅化合物合成方法 26
2-5.1熱蒸鍍法(Thermal Evaporation) 27
2-5.2電漿輔助化學氣相沉積法(Mircowave Plasma Enhanced CVD) 28
2-5.3碳熱還原法(Carbothermal reduction) 32
2-5.4 脈衝雷射蒸鍍法(pulsed laser deposition，PLD) 32
2-5.5水熱法(Hydrothermal) 32
2-5.6溶膠-凝膠法(Sol-Gel method) 33
2-6一維奈米材料的成長機制 34
2-6.1 氣-固(Vapor-Solid mechanism, VS)機制 35
2-6.2氣-液-固(Vapor-Liquid-Solid mechanism, VLS)機制 35
2-6.3溶液-液-固(Solution-Liquid-Solid Mechanism, SLS)機制 39
2-6.4 氧化物輔助成長(Oxide-assisted Growth)機制 40
第三章 實驗方法與儀器介紹 42
3-1實驗流程 42
3-2試片處理 43
3-3合成鋅化合物奈米結構 43
3-3.1 合成氧化鋅奈米柱 43
3-3.2 合成硫化鋅奈米線 44
3-3.3 合成硒化鋅奈米棒 45
3-4儀器介紹 45
3-4.1 微波電漿輔助化學氣相沉積系統 45
3-4-2 場發射掃描式電子顯微鏡(FE-SEM) 47
3-4.3能量散佈光譜(Energy Dispersive Spectrometer, EDS) 48
3-4.4 X光繞射分析儀(XRD) 49
3-4.5 穿透式電子顯微鏡(TEM) 50
3-4-6 X光光電子能譜(XPS) 52
3-4.7 微拉曼光譜儀 53
3-4.8 光激發螢光光譜儀(PL) 54
第四章 結果與討論 56
4-1 氧化鋅的表面形貌分析(SEM) 56
4-1.1 不同形貌的氧化鋅奈米結構 56
4-1.2氧化鋅奈米棒 60
4-1.3 EDS成份分析 62
4-1.4 X光繞射分析(XRD) 64
4-1.5穿透式電子顯微鏡(TEM) 66
4-1.6 X光光電子能譜分析(XPS) 68
4-1.7微拉曼光譜分析(Raman spectroscopy) 70
4-1.8 光致激發(Photoluminescence PL) 71
4-2 硫化鋅的表面形貌 73
4-2.1 硫化鋅奈米線結構 73
4-2.2 硫化鋅奈米線 75
4-2.3 EDS成份分析 76
4-2.4 X光繞射分析(XRD) 78
4-2.5穿透式電子顯微鏡(TEM) 80
4-2.6 X光光電子能譜分析(XPS) 82
4-2.7微拉曼光譜分析(Raman spectroscopy) 84
4-2.8 光致激發(Photoluminescence PL) 86
4-3 硒化鋅的表面形貌 87
4-3.1 硒化鋅奈米棒結構 87
4-3.2 硒化鋅奈米棒 89
4-3.3 EDS成份分析 91
4-3.4 X光繞射分析(XRD) 93
4-3.5穿透式電子顯微鏡(TEM) 95
4-3.6 X光光電子能譜分析(XPS) 97
4-3.7微拉曼光譜分析(Raman spectroscopy) 99
4-3.8 光致激發(Photoluminescence PL) 100
第五章 結論 101
第六章 未來展望 102
第七章 參考文獻 103

[1]Y. H. Kao,"Size-Effect Variation of the Optical Properties of Conductors", Phys. Rev., 144 ,405, (1996).
[2]S. B. Soffer,"Statistical Model for Size Effect in Electrical Conduction",J.Phys., 38,1710,(1967).
[3]J. Schiotz, F. D. D. Tolla, and K.W. Jacobsen ,"Softening of Nanocrystalline Metal at very Small Grain Sizes", Nature, 391, 561(1998).
[4]林聖紘，"藉微波電漿輔助化學氣相沈積系統合成氧化鈦奈米材料與特性分析"，國立清華大學碩士論文，(2006).
[5]R. P. Feynman, "There's Plenty of Room at the Bottom" Pasadena,(1959)
[6]蔡信行，孫光中，"奈米科技導論"，新文京開發出版股份有限公司，(2004)
[7]Avouris, Phaedon, Lyo, In-Whan , Hasegawa, Yukio.,"Probingelectrical transport, electron interference, and quantum size effects at surfaces with STM/STS", IBM Journal of Research & Development,00188646, Nov95 ,Vol, Issue 6
[8]王崇仁，"神奇的奈米科學"，科學發展，354 期，(2006).
[9]NanoScience奈米科學網(http://nano.nchc.org.tw/)
[10]羅聖全，"研發奈米科技的基本工具之一電子顯微鏡介紹SEM "，工業技術研究院材料與化工研究所，(2004).
[11]R. Kubo, "Electronic properties of metallic fine particles.",J. Phys.,975 (1962).
[12]N. Taniguchi, "On the Basic Concept of 'Nanotechnology", Proc. ICPE Tokyo, 2, 18-23 (1974).
[13]G. Binnig, H. Rohrer, C. Gerber, E. Weibel,”Surface studies by scanning tunneling microscopy ”, Phys. Rev. Lett. Vol.49, 57-61 (1982).
[14]G. Binnig, et al.“7×7 Reconstruction on Si(111) Resolved in Real Space”, Phys. Rev. Lett. Vol. 50, 120-123 (1983).
[15]林敏聰，徐斌睿，"近代物理實驗—Scanning Tunneling Microscopy"
[16]M. N. Baibich , J. M. Broto, A. Fert, F. Nguyen Van Dau, F. Petroff,P. Eitenne, G. Creuzet, A. Friederich, J. Chazelas."Giant Magnetoresistance of (001)Fe/(001)Cr Magnetic Superlattices", Phys. Rev. Lett. 61, 2472-2475 (1988).
[17]NEC Corporation, H. W. Kroto, J. R. Heath, S. C. O' Brien, R. F. Curl, R. E. Smalley,"Helical microtubules of graphitic carbon", Nature 354, 56-58 (1991).
[18]D. M. Eigler, and E. K. Schweizer, "Positioning single atoms with a scanning tunnelling microscope", Nature 344, 524-526 (1990).
[19]M. F. Crommie,C. P. Lutz,D. M. Eigler,"Confinement of electrons to quantum corrals on a metal surface" , Science 262, 5131, 218-220,(1993).
[20]Barthoott, W., and C. Neinhuis.,"Purity of the sacred lotus, or escape from contamination in biological surface. "202.1(1997):1-8.
[21]Kim, Philip, and Charles M. Lieber. "Nanotube nanotweezers." Science 286.5447 (1999): 2148-2150.
[22]Choi, W. B., et al. "Fully sealed, high-brightness carbon-nanotube field-emission display." Appl. Phys. Lett 75.20 (1999): 3129-3131.
[23]Novoselov, Kostya S., et al. "Electric field effect in atomically thin carbon films." science 306.5696 (2004): 666-669.
[24]Liu, Chenguang, et al. "Graphene-based supercapacitor with an ultrahigh energy density." Nano Lett.10.12 (2010): 4863-4868.
[25]T. H. Han ,Y. Lee ,M .R. Choi, S.H. Woo, S. H. Bae, B. H. Hong, J. H. Ahn, T.W. Lee, "Extremely efficient flexible organic light-emitting diodes with modified graphene anode", Nature Photonics 6, 105-110 (2012).
[26]林韋辰，"摻雜銻之氧化鋅奈米結構成長與特性分析"，中國文化大學材料科學與奈米科技研究所碩士論文，(2015).
[27]http://www.lchsxp.com/products_detail/productId=30.html
[28]https://detail.1688.com/offer/530424776251.html?spm=a261b.8768355.pic-list.18.ba0d6d99BtAge8
[29]Z. Fan, J.G. Lu , “Zinc Oxide Nanostructures: Synthesis and Properties”, J. Nanosci. Nanotechnol. 5, 1561-1573 (2005).
[30]W. I. Park, Y. H. Jun, S. W. Jung, Gyu-Chul Yi, "Excitonic emissions observed in ZnO single crystal nanorods", Appl. Phys. Lett. 82, 964 (2003).
[31]K. Vanheusden, W. L. Warren, C. H. Seager, D. R. Tallant, J. A. Voigt, "Mechanisms behind green photoluminescence in ZnO phosphor powders", J. Phys.79, 7983 (1996)
[32]P. Yang, H. Yan, S. Mao, R. Russo, J. Johnson, R. Saykally, N. Morris, J. Pham, R. He, H.-J. Choi, "Controlled growth of ZnO nanowires and their optical properties ", Adv. Mater. 12, 323 (2002).
[33]I.Shalish, H. Temkin, and V. Narayanamurti, "Size-dependent surface luminescence in ZnO nanowires", Phys. Rev. B. 69, 245401 (2004).
[34]http://old.b2star.com/news-8325
[35]http://www.baike.com/wiki/%E7%A1%AB%E5%8C%96%E9%94%8C
[36]鄭尹瑋，"利用化學氣相沉積法製備硫化鋅奈米結構及光學性質分析"，中國文化大學，(2010).
[37]http://www.wikiwand.com/zh-tw/%E7%A1%AB%E5%8C%96%E9%94%8C
[38]A.H. Kitai, "Solid State Luminescence" Chapman & Hall, London ,U.K.,(1993).
[39]K. Sooklal ,"Photophysical properties of ZnS Nanoclusters with Spatially Localized Mn2+" J. Phys.100,4551(1996).
[40]丁幸一，"硫化鋅螢光粉製作條件對其發光性質的影響"，逢甲大學化學工程學系碩士論文，(2004).
[41]施敏，張俊彥，"半導體元件物理與製作技術，高立圖書有限公司，(2001).
[42]D. R. Vij, N. Singh," Luminescence and related properties of II-VI semiconductors" Nova Science Publishers, N.Y.(1998)
[43]X. T. Zhang, Y. C. Liu, Z. Z. Zhi, J. Y. Zhang, Y. M. Lu, D. Z. SHEN, and X. G. Kong, "Temperature dependence of excitonic luminescence from nanocrystalline ZnO films" J. of Luminescence,99,149(2002)
[44]K. Vanheusden, W. L. Warren, C. H. Seager, D. R. Tallant, J. A. Voigt, "Green photoluminescence efficiency and free-carrier density in ZnO phosphor powders prepared by spray pyrolysis"J.Phys.46(1996)
[45]https://www.glass.cn/gongyings/1372209.html
[46]http://www.iiviinfrared.com/cn/products/materials_znse.html
[47]J. Basu, R. Divakar ,Julia Nowak, S. Hofmann, A. Colli , A. Franciosi ,and C. Barry Carter ,J .Phys. 104,064302(2008)
[48]X. Dong Yang, Dai Lun, Xu Wan Jin, You Li Ping,"Synthesis and PL Properties of ZnSe Nanowires with Zincblende and Wurtzite Structures "CHIN. PHYS. Lett. vol 23,no.5(2006).
[49]T. Aichele, A. Tribu, C. Bougero, K. Keng ,R. Andre, and S. Tatarenko, " Defect-free ZnSe nanowire and nanoneedle nanostructures" J. Phys. Lett. 93, 143106(2008).
[50]陳峯毅，"不同觸媒對氣相成長硒化鋅一維奈米結構之影響"，台灣科技大學高分子工程研究所碩士論文，(2010).
[51]U. Philipose, T. Xu, S. Yang, P. Sun, Y. Q. Wang and K. L. Kavanagh, "Excitonic and pair-related photoluminescence in ZnSe nanowires", J. Phys. 100, 084316 (2006).
[52]X. T. Zhang,Z. Liu, K. M. Ip, Y. P. Leung, Quan Li, and S. K. Hark, "Luminescence of ZnSe nanowires grown by metalorganic vapor phase deposition under different pressures", J. Phys. volume 95,no.1015,(2004).
[53]U. Philipose, Ping Sun, Tao Xu, and H. E. Ruda, L. Yang and K. L. Kavanagh, "Structure and photoluminescence of ZnSe nanostructures fabricated by vapor phase growth", J. Phys. 101, 014326 (2007).
[54]陳康祺，"五氧化二釩/鉑核殼奈米線之製備與特性研究"，中國文化大學化學工程與材料工程學系奈米材料碩士班碩士論文，(2013).
[55]L. H. Chan, K. H. Hong, S. H. Lai ,X. W. Liu and H. C. Shih, "The formation and characterization of palladium nanowires in growing carbon nanotubes using microwave plasma-enhanced chemical vapor deposition",Thin solid Film, 423,27-32(2003)
[56]張立偉，"低維度氧氮化合物奈米晶體在合成、結構及其光電特性設計與應用之研究"，國立清華大學材料工程學系博士論文，(2011).
[57]洪啟超，"微波電漿系統之氣相及液相合成鑽石膜研究"，國立清華大學材料科學工程研究所，(1996).
[58]薛森鴻，"藉微波電漿輔助化學氣相系統探究氧化鎢"，國立清華大學材料科學與工程研究所，(2004).
[59]Hartanto ,A.B., et al. "Growth mechanism of ZnO nanorods from nanoparticles formed in a laser ablation plume. "Appl .Phys. A 78.3(2004):299-301
[60]https://www.cheaptubes.com/carbon-nanotubes-applications/
[61]D. L. Zhu, H. Zhu, andY. H. Zhang,"Hydrothermal synthesis of La0.5Ba0.5MnO3 nanowires", Appl. Phys. Lett. 80, 1634 (2002).
[62]S. Nishio, M. Kakihana,"Evidence for Visible Light Photochromisum of V2O5", Chem.Mater.,14,3730-3733(2002).
[63]G. Xu, Z. H. Ren, P. Y. Du, W. J. Weng, G. Shen, and G. R. Han,"Polymer assisted hydrothermal synthesis of single crystalline tetragonal perovskite PbZr0.52Ti0.48O3 nanowires ", Adv. Mater. 17, 907-910, (2005).
[64]M. J. Alan, D. C. Cameron, j. Sol-Gel Sci.Tech.25,137-145,(2002).
[65]S. S. Brenner, G. W. Sears,"Mechanism of whisker growth--III nature of growth sites ", Acta Metallurgica 4,268(1956).
[66]Yang, Peidong, and C. M. Lieber,"Nanostructured high-temperature superconductor:Creation of strong-pinning columnar defects in nanorod /superconductor composites ." J. Mater. Res. 12.11 (1997):2981-2996.
[67]J .Zhang, F. Jiang ,"Catalytic growth of Ga2O3 nanowires by physical evaporation and their photoluminescence properties",Chem.Phys. ,289,243-249 (2003).
[68]R. S. Wagner, W. C. Ellis, "Vapor-liquid-solid mechanism of single crystal growth", Appl. Phys. Lett., 4, 89 (1964).
[69]Morales, Alfredo M.,and Charles M .Lieber. "A laser ablation method for the synthesis of crystalline semiconductor nanowires." Science 279.5348(1998): 208-211
[70]M. H. Huang, Y. Wu, H. Feick, N. Tran, E. Weber and P. Yang, "Catalytic growth of zinc Oxide nanowires by vapor transport", Adv. Mater.,13, 113-116 (2001)
[71]Y. Hao, G. Meng, Z. L. Wang, C. Ye, and L. Zhang, "Periodically twinned nanowires and polytypic nanobelts of ZnS: The role of mass diffusion in vapor-liquid-solid Growth", Nano. Lett. , 6,1650-1655 (2006).
[72]Y. Wu, P. Yang ,"Direct observation of vapor-liquid-solid nanowire growth", J. Am. Chem. Soc.,123, 3165-3166 (2001).
[73]林良達，"氧化銦摻雜錫奈米結構之光電特性研究"，中國文化大學材料科學與奈米科技研究所碩士論文，(2011).
[74]T. J. Trentler, K. M. Hickman, S. C. Goel, A. M. Viano, P. C. Gibbons, W. E. Buhro, "Solution-liquid-solid growth of crystalline III-V semiconductors: An analogy to vapor-liquid-solid growth" ,Science, 270, 1797-1794 (1995)
[75]R. Q. Zhang, Y. Lifshitz, S. T. Lee,"Oxide-assisted growth of semiconducting nanowires", Adv. Mater.,15, 635-640 (2003).
[76]W. Bruckner, H. Oppermarm, W. Reichelt, J. I. Ternkow, E. A.Tschudnowski, and E. Wolf, "Vanadium pentoxide I. Structures and properties Vanadiumoxide", Akademie, Berlin, (1983).
[77]H. A. Wriedt, "The O-V (oxygen-vanadium) system", Bull.Alloy Phase. Diagrams, 10, 271-277 (1989).
[78]黃盟文，"低微度奈米金屬化合物結構之合成、特性與應用"，國立中興大學材料工程學系研究所博士學位論文，(2012).
[79]羅聖全，"探索奈米視界,科學基礎研究之重要利器─掃描式電子顯微鏡(SEM)，科學研習 ，(2013).
[80]http://faculty.ndhu.edu.tw/~pgml/SEM_EDS/theory.htm
[81]http://www.toray.cn/trc/kinougenri/kouzou/kou_006.html
[82]https://www.antpedia.com/news/83/n-1477083.html
[83]https://zh.wikipedia.org/wiki/X%E5%B0%84%E7%BA%BF%E5%85%89%E7%94%B5%E5%AD%90%E8%83%BD%E8%B0%B1%E5%AD%A6
[84]http://www.niujin.hk/niujin/Article_Show.aspx?id=74
[85]http://www.mst.or.jp/method/tabid/167/Default.aspx
[86]B. Liu and H. C. Zeng, "Fabrication of ZnO "Dandelions" via a Modified Kirkendall Process ", J. Am. Chem. Soc., 126, p.16744(2004)
[87]Cuscó, Raman, et al. "Temperature dependence of Raman scattering in ZnO."Phys. Rev.B75.16 (2007): 165202.
[88]K. A. Alim, V. A. Fonoberov, A. A. Balandin, "Origin of the optical phonon frequency shifts in ZnO quantum dots",App.Phy.Lett.,vol.86,(2005).
[89]Zeferino R. S., Flores M. B., U. Pal, "Photoluminescence and Raman scattering in Ag-doped ZnO nanoparticles" J. Phys. , (2011), 109(1): 014308
[90]R. Al Asmar, J. P. Atanas, M. Ajaka, et al., "Characterization and Raman investigations on high-quality ZnO thin films fabricated by reactive electron beam evaporation technique ", J. Crys. Growth,(2005), 279(3-4): 394–402
[91]W. J. Li, C. Y. Kong, H. B. Ruan, G.P. Qin, G. J. Huang, T. Y. Yang, W. W. Liang, Y. H. Zhao, X. D. Meng, P. Yu, Y. T. Cui, L. Fang, "Electrical properties and raman scattering investigation of Ag doped ZnO thin films.", Solid State Commun. 152 (2012) 147.
[92]V. Dijken, Addy, et al. "The kinetics of the radiative and nonradiative processes in nanocrystalline ZnO particles upon photoexcitation." J. Phys. Chem. B104.8 (2000): 1715-1723.
[93]Yamamoto, et al. "A novel method for the preparation of green-photo luminescent zinc oxide by microwave-assisted carbothermal reduction." Chem.Lett.33.3 (2004): 246-247.
[94]Vanheusden, K., et al. "Mechanisms behind green-photoluminescence in ZnO phosphor powders." J.Phys.79.10 (1996): 7983-7990.
[95]呂昊穎，氧化鋅及硫化鋅奈米螢光材料之研製及其光電特性之研究，國立成功大學電機工程研究所博士論文，(2005).
[96]Y. C. Cheng, C. Q. Jin, F. Gao, X. L. Wu, W. Zhong, S. H. Li, and P.K. Chu," Raman scattering study of zinc blende and wurtzite ZnS", J. Phys. ,106, 123505 (2009).
[97]S. S. Mitra,"Raman effect in wurtzite and zinc-blende type ZnS single crystals ,Phys. Rev. 171, 931 (1968).
[98]唐超，"不同觸媒對溫度控製成長硫化鋅一維奈米結構之影響"，台灣科技大學高分子工程研究所碩士論文，(2009).
[99]W. Zhou, R. Liu, D. Tang , B. Zou , "The effect of dopant and optical micro-cavity on the photoluminescence of Mn-doped ZnSe nanobelts", Nano. Lett. (2013),8:314
[100]F. F. Wang, Z. H. Zhang, R.B.Liu, X. Z. Wang, "Structure and stimulated emission of ZnSe nanoribbons grown by thermal evaporation". Nanotechnology , (2007) ;8:305705.
[101]陳峯毅，"不同觸媒對氣相成長硒化鋅一維奈米結構之影響"，台灣科技大學高分子工程研究所碩士論文，(2010).
[102]謝佳和，"硒化鋅透光層及浮子成長技術對CulnSe2薄膜太陽能電池特性之影響"，中山大學材料科學研究所，(2002).