臺灣博碩士論文加值系統

本實驗成功製備奈米粒子（Ag或Au奈米顆粒）陣列於表面增強拉曼散射（SERS）基板，並增強待測物分子之表面電漿共振與拉曼信號。在本文中，三明治SERS平台由金/石墨烯奈米片與鋁基板生成多孔陽極氧化鋁（AAO）模板並加入銀奈米粒子（Ag）形成奈米陣列基板所製備。此三明治SERS平台結合Ag / AAO奈米顆粒陣列之SERS效應與金/石墨烯奈米片捕獲生物分子之能力，達到“雙重“SERS增強效應。將檢測的生物分子加入至Ag / AAO奈米顆粒陣列和Au /石墨烯奈米片之間，藉此雙重拉曼增強效應達到快速與穩定放大待測物的拉曼訊號。並藉由穿透式電子顯微鏡、界達電位、X射線繞射儀和X射線光電子能譜儀來分析三明治SERS平台。新型三明治SERS平台具有優異的表面增強拉曼光譜來進行無標記生物檢測，如小生物分子（腺嘌呤（A），胸腺嘧啶（T），胞嘧啶（C），鳥嘌呤（G）的DNA，和β-胡蘿蔔素）和水污染物（孔雀石綠）。

Typical surface-enhanced Raman scattering (SERS) substrates consist of nanoparticles (Ag or Au nanoparticles) arrays, which would supply surface plasmon resonance to enhance the Raman signals of biomolecules close to the “hot spots” of the substrate. In this paper, the sandwich SERS platform has been first created by well-designed nanoarrays of silver nanoparticles (Ag), grown on porous anodic aluminum oxide (AAO) templates (Ag/AAO) and Au/graphene oxide nanosheets. The sandwich SERS platform displays reproducible SERS effect on the well-designed Ag/AAO nanoparticle arrays, and would be flexible to capture the biomolecules on the Au/ graphene nanosheets. The detected biomolecules would be inserted between Ag/AAO nanoparticle arrays and Au/graphene nanosheets to achieve the “reduplicate” Raman-enhanced effect. The characterizations of the sandwich SERS platform would be evaluated by transmission electron microscopy, zeta potential, X-ray diffractometer, and X-ray photoelectron spectroscopy. The novel sandwich SERS platform has excellent Raman enhanced capability to offer great potential for practical applications in the rapid and label-free bio-detection, such as small biomolecules (adenine (A), thymine (T), cytosine (C), guanine (G) from DNA, beta-carotene), water pollutants (malachite green), and biotoxicity of the compound (Aflatoxin B1).

中文摘要 I
Abstract II
目錄 III
圖目錄 VI
表目錄 IX
第一章 緒論 (Introduction) 1
1.1 研究背景 1
1.2 研究目的 2
第二章 文獻回顧 (Literature) 3
2.1 拉曼光譜 3
2.1.1 拉曼光譜的歷史 3
2.1.2 拉曼光譜的原理 4
2.2 表面增強拉曼光譜 6
2.2.1 表面增強拉曼光譜簡介 6
2.2.2 表面增強拉曼效應機制 7
2.3 金奈米粒子 12
2.3.1 金奈米粒子性質與結構 12
2.3.2 金奈米粒子合成方法 14
2.4 石墨烯 16
2.4.1 石墨烯的結構與性質 16
2.4.2 石墨烯的製備方法 18
2.5 聚二甲基二烯丙基氯化銨 23
第三章 實驗 (Experiment) 25
3.1 實驗材料 25
3.2 實驗設備 26
3.3 實驗流程 28
3.4 實驗原理及方法 29
3.4.1 金奈米粒子合成 29
3.4.2 氧化石墨烯合成 30
3.4.3 石墨烯合成 32
3.4.4 Graphene-PDDA合成 32
3.4.5 Au/Graphene-PDDA 34
3.4.6 Ag/AAO奈米粒子陣列合成方法 35
3.4.7 三明治結構金屬奈米粒陣列SERS平台 35
3.4.8 表面增強拉曼光譜實驗 36
3.4.9 儀器分析 38
第四章 結果與討論 (Results and Discussion) 40
4.1 SERS複合材料合成 40
4.1.1 金奈米粒子 40
4.1.2 氧化石墨烯 41
4.1.3 Graphene-PDDA 42
4.1.4 Au/Graphene-PDDA 44
4.1.5 Ag/AAO奈米粒子陣列 50

4.2 SERS效應與應用探討 52
4.2.1 SERS複合材料 52
4.2.2 SERS效應之應用 54
4.2.3 三明治結構金屬奈米陣列SERS平台 59
第五章 結論 (Conclusion) 60
參考文獻 (References) 61
 
圖目錄
Figure 2 1 雷射(488 nm)激發CCl4之拉曼光譜 4
Figure 2 2 雷利與拉曼散射能階示意圖 5
Figure 2 3 金屬奈米粒子LSPR示意圖 8
Figure 2 4 金屬粒子於特定吸收波段之LSPR效應圖 9
Figure 2 5 粒子間距2 nm之二聚體型態銀奈米粒子電磁場效應 10
Figure 2 6 製造銀奈米粒子/多孔性陽極氧化鋁基板流程示意圖 11
Figure 2 7 陽極氧化鋁基板成長銀奈米粒子(a)前(b)後SEM圖(c)銀奈米粒子/陽極氧化鋁基板TEM截面圖 11
Figure 2 8 金奈米粒子結構示意圖 13
Figure 2 9 以檸檬酸鈉熱還原法合成金奈米粒子機制圖 15
Figure 2 10 (a)單層石墨烯示意圖(b)石墨烯之TEM圖 16
Figure 2 11 機械剝離法示意圖 19
Figure 2 12 化學氣相沉積法成長石墨烯示意圖 20
Figure 2 13 氧化石墨烯模型圖 21
Figure 2 14 氧化石墨烯還原後之分子模型 22
Figure 2 15 PDDA之化學結構 23
Figure 2 16 奈米碳管(左)與石墨烯(右) 24
Figure 3 1 實驗總流程圖 28
Figure 3 2 氧化石墨烯合成示意圖 30
Figure 3 3 Graphene-PDDA合成示意圖 32
Figure 3 4 Au/Graphene-PDDA及Ag-AAO奈米粒子陣列三明治夾層示意圖 36
Figure 4 1 金奈米粒子之吸收光譜 40
Figure 4 2 石墨、氧化石墨烯和石墨烯之繞射圖譜 41
Figure 4 3 Graphene oxide及Graphene-PDDA之C(1s)電子能譜圖 43
Figure 4 4 電子能譜分峰圖 (a) Graphene oxide (b) Graphene-PDDA 43
Figure 4 5 Au/Graphene-PDDA奈米複合物流程示意圖 44
Figure 4 6 不同比例Au/Graphene-PDDA TEM圖像 (a) Au 1/G 2 (b) Au 2/G 1 (c) Au 4/G 1 (d) Au 8/G 1 (e) Au 16/G 1 45
Figure 4 7 金奈米粒子粒徑分布圖 46
Figure 4 8 Au/Graphene-PDDA TEM-EDX分析圖 46
Figure 4 9 Au/Graphene-PDDA繞射圖譜 47
Figure 4 10 Graphene oxide、Graphene-PDDA以及金奈米粒子之Zeta potential 49
Figure 4 11 Au/Graphene-PDDA和金奈米粒子之Au4f的電子能譜圖 49
Figure 4 12 不同倍率下的Ag/AAO奈米粒子陣列之SEM圖：(a) AAO (100K), (b) AAO (200K), (c) Ag/AAO (100K), (d) Ag/AAO (200K) 50
Figure 4 13 Ag/AAO奈米粒子陣列之AFM圖(a) AAO (height mode), (b) AAO (3D image), (c) Ag/AAO (height mode), (d) Ag/AAO (3D image) 51
Figure 4 14 in-situ方法合成之Au/Graphene-PDDA TEM圖 53
Figure 4 15 Au/Graphene-PDDA TEM圖 53
Figure 4 16 Au/Graphene-PDDA貼附於生物分子示意圖 54
Figure 4 17 Au/Graphene-PDDA檢測 Adenine稀薄溶液之SERS光譜 54
Figure 4 18 Au/Graphene-PDDA複合物放大所得到β-carotene(20 ppm、10 ppm、5 ppm)之SERS光譜 55
Figure 4 19 不同濃度(10-4~103ppm)之Adenine SERS光譜圖 56
Figure 4 20 不同濃度(0.625-10 ppm) 之孔雀石綠SERS光譜圖 57
Figure 4 21 三明治結構之DNA鹼基對(adenine、thymine、cytosine、guanine) SERS光譜 58
Figure 4 22 孔雀石綠之SERS光譜比較 59

表目錄
Table 3 1 Au/Graphene-PDDA配製比例 34
Table 4 1 石墨、氧化石墨烯、還原氧化石墨烯角度與層間距關係圖 42
Table 4 2 JCPDS資料庫所得之標準Au繞射峰 ( JCPDS Files No. 65-2870) 47

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