臺灣博碩士論文加值系統

[摘要]
本研究主要是利用高溫熱裂解(thermal pyrolysis)的方式，在TOPO-HAD-TOP所建構的溶劑系統中，分別以氧化鎘和硒製備半導體量子點硒化鎘，以及再由硒化鎘為前驅物與硬脂酸鋅製備半導體量子點(quantum dots)硒化鎘/硒化鋅。製程中依據反應時間的長短來控制粒徑大小，並改變不同的鎘和硒莫耳數比來合成硒化鎘量子點。另外，將硒化鎘與發光材料Tb(TMHD)3-DPSO和OC1C8-PPV摻混，研究其光學性質上的差異。
在結構性質的部分，利用紫外光-可見光吸收光譜儀、螢光光譜儀，做光學上的分析及能隙、量子產率計算，以場發射掃描式電子顯微鏡、動態光散射粒徑分析儀，觀察粒徑大小及分布，並利用X光能量散佈光譜儀、X光粉末繞射儀，分析其元素組成及晶體結構。
由實驗結果顯示，硒化鎘量子點為wurtzite結構，屬於六方最密堆積，粒徑約為4-9nm之間，放光波長綠~紅色。隨著反應時間越久，顆粒越大，發光波長也將隨著粒徑而紅位移。當鎘和硒莫耳數比愈小時，波長會有藍位移現象，且可得到粒徑較小的顆粒、量子產率較高。經由硒化鎘包覆一層硒化鋅形成一核殼結構，明顯提升了量子產率。
最後，在硒化鎘摻混發光材料的部分，對Tb(TMHD)3-DPSO而言，可減少雜訊短波長的放光，進而讓材料放光更集中。反觀，對OC1C8-PPV而言，似乎降低了原本材料的吸收強度，不過真正的效果還是要製作成高分子發光二極體(polymer light-emitting diodes, PLED)元件之後，去做量測，才能進一步加以確認。

[Abstract]
The investigations towards CdSe based semiconductor quantum dots are conducted by using CdO and Se as precursors in the TOPO-HAD-TOP solvent system via thermal pyrolysis. Similarly, CdSe and zinc stearate were used as precursors to prepare CdSe/ZnSe based semiconductor quantum dots. Preparations of the semiconductor quantum dots were achieved by changing the molar ratios between Cd and Se. The particle size distribution of the semiconductor quantum dots was found to be reaction time dependent. CdSe were blended with luminescence materials such as Tb(TMHD)3-DPSO and OC1C8-PPV, and the resulting optical properties thus were studied.
The structure properties were obtained by UV-Vis absorption and fluorescence spectroscopy. The properties include the optical analysis, quantum yield, and energy gap. Field-emission scanning electron microscope and dynamic light scattering particle size analyzer were employed to measure the particle size distributions. The elemental compositions and crystalline structures were demonstrated by X-ray energy dispersive spectrometer and X-ray powder diffractometer.
The semiconductor quantum dots were found to be a wurtzite structure (hexagonal closet packing). The particle size distribution was determined to be 4~9nm with a green to red emission color. The particle of the semiconductor quantum dots gets bigger when the reaction time is elongated. A red shift of the emission wavelength was also observed. However, the particle of the semiconductor quantum dots gets smaller when the molar ratio between Cd and Se gets smaller. A blue shift of the emission wavelength and higher quantum yield are observed. CdSe with a ZnSe core-shell leads to a higher quantum yield.
When CdSe was blended with Tb(TMHD)3-DPSO luminescence material, the emission at the short wavelength decreased and the strength at the emission wavelength gets more focused. The emission intensity is reduced with the blending of OC1C8-PPV luminescence material, and the effects on the corresponding PLED devices still need further studies.

[目錄]
中文摘要......................................................I
英文摘要....................................................III
謝誌..........................................................V
目錄.........................................................VI
圖目錄........................................................X
表目錄.....................................................XIII
第一章 緒論...................................................1
1-1 前言......................................................1
1-2 奈米材料簡介..............................................4
1-3 量子點簡介................................................7
1-4 奈米效應..................................................9
1-4-1 小尺寸效應..............................................9
1-4-2 量子尺寸效應...........................................10
1-4-3 量子侷限效應...........................................11
1-4-4 表面效應...............................................13
1-5 硒化鎘之能隙、粒徑與螢光相對量子產率計算.................14
1-5-1 硒化鎘能隙計算.........................................14
1-5-2 硒化鎘粒徑計算.........................................14
1-5-3 硒化鎘螢光相對量子產率計算.............................16
1-6 有機發光二極體原理.......................................18
1-7 文獻回顧.................................................20
1-7-1 半導體量子點的製備與發展...............................20
1-7-2 半導體量子點核殼結構的設計.............................25
1-7-3 半導體量子點核殼結構的製備與發展.......................25
1-7-4 半導體量子點核殼結構的改質應用.........................26
1-7-5 半導體量子點在有機發光二極體應用.......................29
1-8 研究動機.................................................30
第二章 實驗部分..............................................32
2-1 研究流程.................................................32
2-2 儀器部分.................................................32
2-3 實驗藥品.................................................35
2-4 實驗架構.................................................37
2-5 實驗步驟.................................................38
2-6 分析方法.................................................44
第三章 結果與討論............................................48
3-1 CdSe之合成...............................................48
3-1-1 紫外光-可見光吸收光譜儀................................48
3-1-2 螢光光譜儀.............................................49
3-1-3 動態光散射粒徑分析儀...................................50
3-1-4 X光粉末繞射儀..........................................51
3-1-5 掃描式電子顯微鏡-X光能量散佈光譜儀.....................52
3-1-6 場發射掃描式電子顯微鏡.................................52
3-2 CdSe/ZnSe之合成..........................................53
3-2-1 紫外光-可見光吸收光譜儀................................53
3-2-2 螢光光譜儀.............................................54
3-2-3 動態光散射粒徑分析儀...................................54
3-2-4 X光粉末繞射儀..........................................55
3-2-5 掃描式電子顯微鏡-X光能量散佈光譜儀.....................55
3-2-6 場發射掃描式電子顯微鏡.................................56
3-3 CdSe 摻混發光材料........................................57
3-3-1 CdSe摻混Tb(TMHD)3-DPSO.................................57
3-3-2 CdSe摻混OC1C8-PPV......................................58
第四章 結論及未來研究方向....................................80
4-1 結論.....................................................80
4-2 未來研究方向.............................................81
參考文獻.....................................................82
附錄.........................................................88
自述.........................................................89

[圖目錄]
圖1-1 量子點的光性質..........................................3
圖1-2 A.Core/Shell TEM圖 B.改質後多層QDs的結構...............3
圖1-3 材料歷史演進過程........................................6
圖1-4 奈米材料之製備方式......................................6
圖1-5 CdSe量子點結構及尺寸大小................................8
圖1-6 材料尺寸大小和能階關係.................................11
圖1-7 不同維度的能帶結構.....................................12
圖1-8 金屬與半導體能帶分裂型態...............................12
圖1-9 表面原子數之比例與粒徑關係.............................13
圖1-10 有機發光二極體的基本結構圖............................19
圖1-11 有機發光二極體的發光原理..............................19
圖1-12 奈米晶體的成核過程及反應裝置..........................23
圖1-13 不同粒徑大小的CdSe奈米微粒其UV和PL圖譜................23
圖1-14 CdS隨著不同的OA濃度其時間和UV波長的關係...............24
圖1-15 半導體材料的晶格參數差異度和能隙......................24
圖1-16 以mercaptoacetic acid修飾CdSe/ZnS鍵結蛋白質分子圖示...27
圖1-17 連結劑的結構..........................................28
圖2-1 半導體量子點CdSe和CdSe/ZnSe之合成分析與性質研究流程圖..34
圖2-2 CdSe之合成流程圖.......................................42
圖2-3 CdSe/ZnSe之合成流程圖..................................42
圖3-1 不同時間點的CdSe反應液以UV燈365nm照射..................59
圖3-2 標準品Rhodamine 6G的光譜圖.............................59
圖3-3 CdSe反應時間和顏色關係(Cd/Se = 1/1.25).................60
圖3-4 CdSe反應時間和顏色關係(Cd/Se = 1/5)....................60
圖3-5 CdSe之UV-Vis圖(Cd/Se = 1/1.25).........................61
圖3-6 CdSe之UV-Vis圖(Cd/Se = 1/5)............................61
圖3-7 CdSe之螢光光譜圖(Cd/Se = 1/1.25).......................63
圖3-8 CdSe之螢光光譜圖(Cd/Se = 1/5)..........................63
圖3-9 CdSe之動態光散射粒徑分析儀數據(Cd/Se = 1/1.25).........65
圖3-10 CdSe之動態光散射粒徑分析儀數據(Cd/Se = 1/5)...........65
圖3-11 CdSe之XRD圖(Cd/Se = 1/1.25)...........................66
圖3-12 CdSe之XRD圖(Cd/Se = 1/5)..............................66
圖3-13 CdSe之EDS圖(Cd/Se = 1/1.25)...........................67
圖3-14 CdSe之EDS圖(Cd/Se = 1/5)..............................67
圖3-15 CdSe之FE-SEM圖(Cd/Se = 1/1.25)150K....................68
圖3-16 CdSe之FE-SEM圖(Cd/Se = 1/1.25)200K....................68
圖3-17 CdSe之FE-SEM圖(Cd/Se = 1/5)100K.......................69
圖3-18 CdSe/ZnSe反應時間和顏色關係...........................70
圖3-19 ZnSe的UV和螢光光圖譜..................................70
圖3-20 CdSe/ZnSe之UV光譜圖...................................71
圖3-21 CdSe/ZnSe之螢光光譜圖.................................71
圖3-22 單獨針對CdSe和CdSe/ZnSe螢光光譜圖比對.................72
圖3-23 CdSe/ZnSe之動態光散射粒徑分析儀數據...................73
圖3-24 CdSe/ZnSe之XRD圖......................................73
圖3-25 CdSe/ZnSe之EDS圖......................................74
圖3-26 CdSe/ZnSe之FE-SEM圖(120K).............................74
圖3-27 CdSe/ZnSe之FE-SEM圖(150K).............................75
圖3-28 發光材料的UV圖........................................76
圖3-29 發光材料的螢光光譜圖..................................76
圖3-30 添加1%CdSe到Tb(TMHD)3-DPSO中其螢光光譜圖..............77
圖3-31 添加3%CdSe到Tb(TMHD)3-DPSO中其螢光光譜圖..............77
圖3-32 添加5%CdSe到Tb(TMHD)3-DPSO中其螢光光譜圖..............78
圖3-33 添加20%CdSe到OC1C8-PPV中其螢光光譜圖..................78
圖3-34 添加40%CdSe到OC1C8-PPV中其螢光光譜圖..................79
圖3-35 添加60%CdSe到OC1C8-PPV中其螢光光譜圖發光..............79

[表目錄]
表1-1 常見半導體量子點的種類..................................3
表1-2 常見無機core/shell結構..................................3
表1-3 各種奈米等級物質的型態..................................6
表1-4 材料尺度的分類.........................................10
表1-5 物種的能隙、電子電洞有效質量、介電常數值...............16
表1-6 各種無機奈米粒子和生物分子的連結.......................28
表2-1 QDs摻混到發光材料比例表................................43
表2-2 CdSe和ZnSe JCPDS的相關資料.............................46
表3-1 CdSe反應時間和顏色的關係...............................59
表3-2 CdSe之UV-Vis光譜數據與粒徑大小(Cd/Se = 1/1.25).........62
表3-3 CdSe之UV-Vis光譜數據與粒徑大小(Cd/Se = 1/5)............62
表3-4 CdSe之螢光光譜圖數據(Cd/Se = 1/1.25)...................64
表3-5 CdSe之螢光光譜圖數據(Cd/Se = 1/5)......................64
表3-6 CdSe/ZnSe的光學性質數據及量子產率......................72

[參考文獻]
1. S. Dalmassoa et al., “MBE grown InGaN quantum dots andquantum wells:effects of in-plane localization.” Thin solid films, 380, 195-197 (2000).
2. K. Molnar et al., “Characterization of ITO/porous silicon LED structures.” Journal of luminescence, 80, 91-97 (1999).
3. H. M. Lin et al., “Nanocrystalline WO3-based H2S sensors.” Sensors & Actuators: B Chemical, 22, 63-68 (1994).
4. H. M. Lin, T. Y. Hsu, C. Y. Tung, C. M. Hsu, “Hydrogen sulfide detection by nanocrystal PT doped TiO2-based gas sensors.” Nanostrustured mterials, 6, 1001-1004 (1995).
5. M. B. Jr. et al., "Semiconductor nanocrystals as fluorescent biological labels.” Science, 281, 2013-2015 (1998).
6. W. C. W. Chan, S. Nie, “Quantum dot bioconjugates for ultrasensitive nonisotopic detection.” Science, 281, 2016-2018 (1998).
7. 楊正義、陳吉峰、葉怡均、陳正龍、陳家俊，「金屬、半導體奈米晶體在生物檢測及分析上的應用」，物理雙月刊，23卷6期(90年12月)，頁667-677。
8. 馬振基著，奈米材料科技原理與應用，台北市：全華，民92。
9. A. Watson, X. Wu, M. Bruchez, “Lighting up cells with quantum dots.” Biotechniques, 34(2), 296-303 (2003).
10. D. Gerion et al., “Synthesis and properties of biocompatible water-soluble silica-coated CdSe/ZnS semiconductor quantum dots.” J. Phys. Chem. B, 105, 8861-8871 (2001).
11. G. P. Mitchell, C. A. Mirkin, R. L. Letsinger, “Programmed assembly of DNA functionalized quantum dots.” J. Am. Chem. Soc., 121, 8122-8123 (1999).
12. 王宏文、林孟萱，「Core-shell奈米粒子的合成技術」，工業材料雜誌，190期(91年10月)，頁96-104。
13. X. Peng, M. C. Schlamp, A. V. Kadavanich, A. P. Alivisatos, “Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility.” J. Am. Chem. Soc., 119, 7019-7029 (1997).
14. M. A. Malik, P. O’Brien, N. Revaprasadu, “A simple route to the synthesis of core/shell nanoparticles of chalcogenides.” Chem. Mater., 14, 2004-2010 (2002).
15. 牟中原、陳家俊，「奈米材料研究發展」，科學發展月刊，28卷4期(89年4月)，頁281-288。
16. 張立德、牟季美合著，奈米材料和奈米結構，台中市：滄海，民91。
17. 陳學士，「量子點簡介」，化工科技與商情，36期。
18. 廖建勛，「奈米複合材料」，九十四年度複合材料/特用化學人才培訓計畫，財團法人自強工業科學基金會，94年11月23日。
19. 黃合建，「光敏性硒化鎘奈米微粉之合成與特性研究」，國立成功大學化學工程學系碩士論文，93年6月。
20. A. D. Yoffe, “Low-dimensional systems: Quantum size effects and electronic properties of semiconductor microcrystallites (zero-dimensional systems) and some quasi-two-dimensional systems.” Adv. Phys., 42(2), 173-266 (1993)
21. L. E. Brus, “Electron-electron and electron-hole interactions in small semiconductor crystallites: The size dependence of the lowest excited electronic state.” J. Chem. Phys., 80(9), 4403-4409 (1984).
22. R. Rossetti, J. L. Ellison, J. M. Gibson, L. E. Brus, “Size effects in the excited electronic states of small colloidal CdS crystallites.” J. Chem. Phys., 80(9), 4464-4469 (1984).
23. H. Sato, T. Hirai, I. Komasawa, “Mechanism of formation of composite CdS-ZnS ultrafine particles in reverse micelles.” Ind. Eng. Chem. Res., 34(7), 2493-2498 (1995).
24. A. L. Linsebigler, G. Lu, J. T. Y. Jr., “Photocatalysis on TiO2 surfaces: Principles, Mechanisms, and Selected results.” Chem. Rev., 95(3), 735-758 (1995).
25. A. L. Rogach et al. “Synthesis and characterization of a size series of extremely small thiol-stabilized CdSe nanocrystals.” J. Phys. Chem. B, 103, 3065-3069 (1999).
26. D. Schooss, A. Mews, A. Eychmuller, H. Weller, “Quantum-dot quantum well CdS/HgS/CdS: Theory and experiment.” Physical review B, 49(24), 17072-17078 (1994).
27. P. Reiss, J. Bleuse, A. Pron, “Highly luminescent CdSe/ZnSe core/shell nanocrystals of low size dispersion.” Nano Lett., 2(7), 781-784 (2002).
28. L. Qu, X. Peng, “Control of photoluminescence properties of CdSe nanocrystals in growth.” J. Am. Chem. Soc., 124(9), 2049-2055 (2002).
29. C. de M. Donega et al. “Single-step synthesis to control the photoluminescence quantum yield and size dispersion of CdSe nanocrystals.” J.Phys.Chem.B, (107), 489-496 (2003).
30. 顧鴻壽著，光電有機電激發光顯示器，台北縣：新文京，民90。
31. 呂伯彥、古俊能，「OLED元件技術」，工業技術研究院，90年4月25日。
32. 張敏忠、陳來成，「PLED顯示器材料及現況和PLED元件及製程」，財團法人自強工業科學基金會，91年5月16日。
33. 李俊育，「CdSe-高分子複合薄膜之電機發光元件」，國立中正大學物理系碩士論文，92年7月。
34. C. B. Murray, D. J. Norris, M. G. Bawendi, “Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites.” J. Am. Chem. Soc., 115, 8706-8715 (1993).
35. Z. A. Peng, X. Peng, “Formation of high-quality CdTe, CdSe, and CdS nanocrystals using CdO as precursor.” J. Am. Soc. Chem., 123, 183-184 (2001)
36. L. Qu, Z. A. Peng, X. Peng, “Alternative routes toward high quality CdSe nanocrystals.” Nano. Lett., 6, 333-337 (2001).
37. W. W. Yu, X. Peng, “Formation of high-quality CdS and Other Ⅱ-Ⅵ semiconductor nanocrystals in noncoordinating solvent: Tunable reactivity of monomers.” Angew. Chem. Int. Ed., 41(13), 2368-2371 (2002).
38. X. Peng, J. Wickham, A. P. Alivisatos, “Kinetics of Ⅱ-Ⅵ and Ⅲ-Ⅴ colloidal semiconductor nanocrystal growth: “Focusing” of size distributions.” J. Am. Chem. Soc., 120, 5343-5344 (1998).
39. T. Trindade, P. O’Brien, “Synthesis of CdS and CdSe nanoparticles by thermolysis of diethyldithio- or diethyldiseleon- carbamates of cadmium.” J. Mater. Chem.,6(3), 343-347 (1996).
40. T. Trindade, P. O’Brien, “Synthesis of CdS and CdSe nanocrystallites using a novel single-molecule precursors approach.” Chem. Mater., 9(2), 523-530 (1997).
41. X. Peng et al., “Shape control of CdSe nanocrystals.” Nature, 404, 59-61 (2000).
42. Z. A. Peng, X. Peng, “Nearly monodisperse and shape-controlled CdSe nanocrystals via alternative routes: Nucleation and growth.” J. Am. Chem. Soc.,124(13), 3343-3353 (2002).
43. X. Peng, “Mechanisms for the shape-control and shape-evolution of colloidal semiconductor nanocrystals.” Adv. Mater., 15(5), 459-463 (2003).
44. M. A. Hines, P. G. Sionnest, “Synthesis and characterization of strongly luminescing ZnS-Capped CdSe nanocrystals.” J. Phys. Chem., 100, 468-471 (1996).
45. B. O. Dabbousi et al., “(CdSe)ZnS core-shell quantum dots: Synthesis and characterization of a size series of highly luminescent nanocrystallites.” J. Phys. Chem. B, 101, 9463-9475 (1997).
46. D. V. Talapin et al., “Highly luminescent monodisperse CdSe and CdSe/ZnS nanocrystals synthesized in a hexadecylamine, trioctylphosphine oxide, trioctylphospine mixture.” Nano. Lett., 1(4), 207-211 (2001).
47. I. Mekis et al., “One-pot synthesis of highly luminescent CdSe/CdS core-shell nanocrystals via organometallic and “Greener” chemical approaches.” J. Phys. Chem. B, 107, 7454-7462 (2003).
48. D. M. Willard, L. L. Carillo, J. Jung, A. V. Orden, “CdSe-ZnS quantum dots as resonance energy transfer donors in a model protein-protein binding assay.” Nano. Lett., 1(9), 469-474 (2001).
49. C. B. Murray, C. R. Kagan, M. G. Bawendi, “Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies.” Annu. Rev. Mater. Sci., 30, 545-610 (2000).
50. C. M. Niemeyer, “Nanoparticles, Proteins, and Nucleic acids: Biotechnology meets materials science.” Angew. Chem. Int. Ed., 40, 4128-4158 (2001).
51. M. Han, X. Gao, J. Z. Su, S. Nie, ”Quantum-dot-tagged micro beads for multiplexed optical coding of biomolecules.” Nature biotechnology, 19, 631-635 (2001).
52. 王子賢、李文乾，「生醫生化用途之奈米微粒」，化工，50卷2期(92年4月)，頁44-53。
53. 謝孟婷，「有機/無機量子點在OLED之應用」，電子與材料雜誌，28期，(94年11月)，頁89-94。
54. 林麗娟，「X光繞射原理及其應用」，工業材料，86期，(83年2月)，頁100-109。
55.「奈米材料應用與奈米元件技術」，財團法人自強工業科學基金會，91年10月。