臺灣博碩士論文加值系統

藉由改變硝酸銀溶液和還原劑(硼氫化鈉)的濃度，我們可以利用化學還原法獲得8nm ~ 78nm尺寸範圍的奈米銀顆粒，並觀察這些不同尺寸銀顆粒在476nm~633nm六種不同入射光波長下對表面增強拉曼光譜(SERS)的影響。SERS的量測對象為濃度10-2 M之苯甲酸(BA)甲醇溶液的1003 cm-1和1600 cm-1 振動模，並以其相對於甲醇1028 cm-1振動模的譜線高度為SERS相對強度。
實驗發現，隨著硝酸銀溶液的濃度不同，溶液的顏色也有所不同，銀顆粒大小也有所不同，而BA振動模的SERS相對強度隨著奈米銀顆粒尺寸增加而跟著增加。然而各尺寸銀顆粒的最佳的入射波長都集中在500nm附近，雖然隨著奈米銀顆粒尺寸增加有著紅位移的現象，但卻不明顯。
Schatz的電磁理論曾針對單顆銀顆粒提出在不同入射光波長、銀顆粒形狀和尺寸的SERS強弱變化。我們發現，除了尺寸為8nm的數據外，實驗的結果與理論所推估出的尺寸對SERS強度影響趨勢相當契合，推論是古典電磁理論不適用太小銀顆粒尺寸所致；而Schatz推論8nm~78nm的最佳波長在360nm~400nm，雖然隨著銀顆粒尺寸增加有紅位移的情況，然而在定量上則明顯與實驗不同。

By changing the concentrations of silver nitrate solutions and reducing agents (sodium borohydride),we could obtain the silver particles with sizes ranging from 8nm to 78nm and observe the particle’s size-effect on the Surface Enhanced Raman Scattering (SERS) of benzoic acid(BA) solutions excited by six laser wavelengths(476nm~633nm). The BA is dissolved in methanol and kept at the concentration 10-2 M。We analyzed the intensities of BA’s 1003 cm-1 and 1600 cm-1 vibrational modes relative to the 1033 cm-1 vibrational mode of methanol.
The observed size-dependences of SERS intensities fit quite well with those calculated by the Schatz’s theoretical model for the spherical silver nanoparticles. The only exception occurred for the cases with the smallest particles (8nm), possibly due to the failure of Maxwell EM theories used in this model.
As predicted by Schatz’s model, our experimental results of BA’s SERS intensity exhibit a maximum at the optimum excitation wavelength for either small or large silver nanoparticles. However, the optimum wavelengths deviate quantitatively from the theoretical estimations.

目錄
誌謝 i
摘要 ii
Abstract iii
目錄 iv
圖目錄 vi
表目錄 xii
第一章　序論 1
1.1 前言 1
1.2 研究動機 4
1.3 論文架構 5
第二章　原理簡介 6
2.1 拉曼散射 6
2.2 表面增強拉曼散射 10
第三章　實驗方法 11
3.1 實驗儀器與架構 12
3.1.1 實驗儀器 12
3.1.2 實驗架構 14
3.2 實驗樣品配製與結果呈現 16
3.2.1 實驗藥品 16
3.2.2待測分子 17
3.2.3硝酸銀與硼氫化鈉的還原反應 18
3.2.4穩定劑 19
3.2.5還原奈米銀顆粒與製備待測樣品 21
3.2.6待測樣品的溶液圖片 24
3.2.7製備TEM樣品與TEM照片顯示銀顆粒的大小 28
第四章　Schatz的理論模型 31
4.1 Schatz理論推導 31
4.2 MatLAB計算結果 36
4.3 MatLAB程式碼 40
第五章　實驗結果與討論 55
5.1 原始光譜數據圖 55
5.2奈米銀顆粒對單一顆粒與單位面積的歸一化 62
5.3銀顆粒尺寸和激發光波長對SERS的影響 67
5.3.1 單一銀顆粒尺寸與不同入射波長比較 67
5.3.2 單一入射波長與不同銀顆粒尺寸比較 72
第六章　結論與未來工作 87
參考文獻 89

參考文獻
1.Fleischmann M, Hendra PJ, McQuillan AJ, J. Chem. Phys. Lett. 1974; 26: 163.
2.Vlckova B, Pavel I, Sladkova M, Siskova K, Slouf M, Journal of Molecular Structure, 2007；834-836：42-47.
3.Chen K, Vo-Dinh KC, Yan F, Wabuyele MB, Vo-Dinh T, Analytica Chimica Acta, 2006; 569: 234-237.
4.Jia TJ, Li PW, Shang ZG, Zhang L, He TC,Mo YJ, Journal of Molecular Structure , 2008; 873: 1-4.
5.Kumar R, Zhou H, Cronin SB, APPLIED PHYSICS LETTERS, 2007; 91: 223105.
6.Quagliano LG, Surface Science, 2004；566-568: 875-879.
7.Choi SH, Wang D, Williams JR, Park M, Lu W, Dhar S and Feldman LC, Applied Surface Science, 2007 ; 253: 5411-5414.
8.Li ZM, Zhang N, Li FT, Applied Surface Science, 2006; 253: 2870–2874.
9.Bao L, Mahurin SM, Haire RG, and Dai S, Analytical Chemistry, 2003; 75, 6614-6620.
10.Bozzini B, Mele C, and Romanello V, Journal of Electroanalytical Chemistry, 2006; 592: 25-30.
11.Pavan Kumar GV, Shruthi S, Vibha B, Ashok Reddy BA, Kundu TK, and Narayana C, J. Phys. Chem. C, 2007; 111: 4388-4392.
12.Schopf JW, Kudryavtsev AB, Agresti DG, Wdowiak TJ and Czaja AD, Nature , 2002; 416: 73-76.
13.Kim K, Kim NH, Park HK, Biosensors and Bioelectronices, 2007; 22: 1000-1005.
14.Zeman EJ, Schatz GC, J. Phys. Chem., 1987; 91: 634-643.
15.Bozlee B, JOURNAL OF RAMAN SPECTROSCOPY, 1996; 27: 75-82.
16.Sandrock ML, JOURNAL OF PHYSICAL CHEMISTRY B, 1999; 103 (14): 2668-2673.
17.Pan DB, CHEMICAL PHYSICS LETTERS, 1997; 275(3-4): 227-233.
18.Haes AJ, J. Phys. Chem. B, 2004; 108: 109-116.
19.Yang Y, Matsubara S, Xiong L, Hayakawa T, and Nogami M, J. Phys. Chem. C, 2007; 111: 9095-9104.
20.Lisiecki I, Billoudet F, and Pileni MP, J. Phys. Chem., 1996; 100: 4160-4166.
21.Wei A, CHEMPHYSCHEM, 2001; 12: 743-745.
22.Foss CA, J. Phys. Chem., 1994; 98: 2963-2971.
23.Zhang WW, Journal of Colloid and Interface Science, 2003; 268: 173-180.
24.Roark SE, ANALYTICA CHIMICA ACTA, 1995; 307: 341-353.
25.Aussenegg FR, Lippitsch ME, Chem. Phys. Lett. 1978, 59: 214.
26.Otto A, J. Raman Spectrosc. 1991, 22: 743.
27.Lili X, Yan F, Spectrochimica Acta PartA, 2005; 61: 1991-1995.
28.Kerker M, J. Opt. Soc. Am. B, 1985; 2: 1327-1329.
29.Blatchford CG, Surf. Sci., 1982; 120: 435-455.
30.Weitz DA, Opt. Lett., 1982; 7: 168-170.
31.Driskell JD, J. Phys. Chem. B, 2006; 110: 17444-17451.
32.Huang BR, Chen KH, Ke WZ, Materials Letters, 2000; 42: 162-165.
33.Miranda MM, Pergolese B, Bigotto A, Giusti A, Innocenti M, Mater Science and Engineering C, 2007; 27: 1295-1299.
34.McLellan JM, Siekkinen A, Chen J, Xia Y, Chem. Phys. Lett., 2006; 427: 122-126 .
35.Zhao Y, Jiang Y, Fang Y, Spectrochimica Acta Part A, 2006; 65: 1003-1006.
36.Badr Y, Mahmoud MA, Journal of Molecular Structure, 2005; 749: 187-192.
37.Glavee GN, Klabunde KJ, Sorensen CM, Hadjapanayis GC, Langmuir, 1992; 8: 771-773.
38.Barnickel P, Wokaun A, Sager W, and Eicke HF, Journal of Colloid and Interface Science, 1992; 148: 80-90.
39.Medendrop NW, Jr., Boeman KJ, Trumble KP, Materials Science Engineering, 1996; A212: 222-227.
40.Widoniak J, Assmann SE, Maret G, Colloids and Surfaces A: Physicochem. Eng. Aspects, 2005; 270-271: 340-344.
41.Zhu ZH, NANOTECHNOLOGY, 2004; 15 (3): 357-364.
42.Xu H, Physical Review E, 2000; 62: 3.
43.Emory SR, Haskins WE, and Nie S, J. Am. Chem. Soc., 1998; 120: 8009-8010.