臺灣博碩士論文加值系統

由於表面增強拉曼散射效應能夠大幅提升分析化學物質的靈敏度，因此本研究利用無電極置換法及用具有特殊光化學性質之半導體ZnS及ZnSe晶體為基材，以簡單操作及設備製作具有表面增強拉曼散射活性的基板。此方法是利用基材本身與溶液中金屬離子的氧化還原電位差，使金屬奈米粒子自發性的生成於基材表面，並配合適當之熱、光輔助法及添加劑作用，還原金離子修飾於晶體上。為了探討不同反應條件對生成的金屬材料影響，以pHydroxythiophenol (pHTP)為指標分子，藉由拉曼訊號及對應之SEM影像，了解製備出的金奈米基材的形態與性質對拉曼訊號增強效果的影響，再進一步開發出增強基板。
從實驗結果得知，以熱輔助法可製備金奈米粒子於ZnS及ZnSe晶體上，並分別添加1 mM及 3 mM PVP控制粒子型態即可獲得典型的SERS光譜，使訊號強度最佳至4076(±340) counts及50022(±2756) counts；然而使用光輔助法所獲得的粒子，經EDS元素分析後得知其生成AuxSy及AuxSey複合物於粒子表面，即使利用添加劑控制型態，仍有機會影響到訊號增強的表現，以目前實驗結果當添加3 mM EDTA於ZnS光輔助反應中，最佳訊號強度為1027(±236)，使用PVP於ZnSe光化學輔助反應中，最佳訊號強度為11287(±796) counts，但經過pHTP吸附或是水煮等方法，有效去除部分的複合物，因此訊號表現也與粒子的粒性、型態等性質有關，可對照SEM影像了解其相關性。
另外，對照第三及第四章實驗結果，使用PVP及EDTA於溶液中，經熱輔助及光化學輔助法生成之粒子型態及訊號趨勢可以得知，使用不同晶體及置備方法，可生成出不同形態之金奈米粒子，進而影響基材對於指標分子訊號增強的效果，因此需挑選適當實驗條件製作出良好的SERS活性基材。
最後，兩者晶體以最佳條件下製備SERS基材的增強因子分別為，添加1 mM PVP於ZnS熱輔助法並反應30分鐘之EF值為4.6(±0.5)×106；而添加3 mM PVP於ZnSe熱輔助法並反應42分鐘之EF值為4.6(±0.8)×107。

Surface-enhanced Raman scattering (SERS) is a powerful means for chemical analysis. This SERS effect can be observed when target molecules adsorbed or nearby metal nanoparitcles with a proper size and shape. To prepare active substrates for SERS measurements, ZnS and ZnSe crystals were selected as solid support in this work as they are commonly used optical windows, which exhibit photocatalytic ability with unique chemical properties. Methods based on electroless displacement and the assistance of photoreduction were developed to decorate SERS active gold nanoparticles (AuNPs) on the selected ZnS and ZnSe crystals. Several parameters, such as the concentration of reaction solution, the temperature of reaction, photo irradiation time, and the additive, were examined their contributions to the production of suitable AuNPs for SERS measurements. pHydroxythiophenol (pHTP) was used to probe the SERS performances for the prepared SERS substrates. After correlation of the observed Raman signals, the morphology of produced AuNPs by SEM with reaction parameters, mechanisms in production of AuNPs on ZnS and ZnSe were found significantly different. For produced AuNPs on ZnS crystal, AuxSy particles were formed rather than AuNPs, which degraded their SERS performances. On the other hand, when ZnSe crystals were used, Se atoms in the ZnSe crystals are capable to reduce the gold ions through formation of higher oxidation state of Se and hence, AuxSe particles formed on the surface of ZnSe is limited. On the other hand, SERS substrates based on ZnSe showed much better performances than that of ZnS. By tuning the reaction conditions, SERS substrates based on ZnS and ZnSe could be successfully prepared. Based on the optimized condition in preparation of SERS substrates, SERS intensity of pHTP on ZnS substrate was found an order weaker than that of ZnSe. In conclusion, a new method to prepare AuNPs on ZnS and ZnSe was successfully developed in this work and both the mechanism in formation and the impact of each parameter to the formation of AuNPs were well explored.

摘要 i
Abstract ii
總目錄 iii
圖目錄 vi
表目錄 xvi
第一章 序論 1
1-1 前言 1
1-2 表面增強拉曼效應的應用 2
1-3 表面增強拉曼散射之金屬奈米粒子由上而下法製作 3
1-4表面增強拉曼散射之金屬奈米粒子由下而上法製作 3
1-4-1 蒸鍍法(Deposition)： 3
1-4-2 溶膠-凝膠法(Sol-Gel)： 3
1-4-3 分子自組裝(Molecular self-assembly)： 4
1-4-4電化學方法(Electrochemistry)： 4
1-4-5 化學還原法： 4
1-4-6 無電極置換法(Electroless deposition)： 5
1-5 研究動機 6
第二章 實驗部分 9
2-1 光學儀器與設備 9
2-3 藥品配製 11
2-4 金奈米粒子之製備方法 12
2-4-1 晶體拋光清洗： 12
2-4-2 無電極置換法： 12
2-4-3 光還原輔助法製備法： 12
2-5 UV光照系統設置與規格： 13
2-6 拉曼光譜測量與設定： 13
2-7 紫外-可見光光譜測量與設定： 13
第三章 光熱輔助法在ZnS晶體表面修飾金奈米材料的效果探討 16
3-1 前言 16
3-2 指標分子基礎探討 16
3-3 熱輔助法對製備金奈米基材之效果探討 19
3-3-1 開放性容器 19
3-3-2 密閉容器 23
3-4添加劑於熱輔助法對金奈米基材之效果探討 31
3-4-1添加劑種類於熱輔助法對金奈米基材之效果 33
3-4-2 PVP濃度於熱輔助法對金奈米基材之效果 39
3-4-3 EDTA濃度於熱輔助法對金奈米基材之效果 43
3-4-4 添加劑於熱輔助法對金奈米粒子生成於ZnS基材之元素組成探討 43
3-5 光化學輔助法與金溶液濃度對金奈米粒基材之探討 46
3-6 添加劑於光化學輔助法對金奈米基材之效果探討 52
3-6-1 添加劑種類於光化學輔助法對金奈米基材之效果 52
3-6-2 EDTA濃度於光化學輔助法對金奈米基材之效果探討 58
3-6-3 PVP濃度於光化學輔助法對金奈米基材之效果 64
3-6-4 添加劑於光輔助法對金奈米粒子生成於ZnS基材之元素組成探討 67
3-7 於ZnS表面製備金奈米粒子SERS基材的訊號增益倍率 72
3-8 結論 74
第四章 光熱輔助法在ZnSe晶體表面修飾金奈米材料的效果探討 75
4-1 前言 75
4-2 指標分子基礎探討 75
4-3 熱輔助法對製備金奈米基材之效果探討 77
4-3-1 開放容器 77
4-3-2 密閉容器 80
4-4添加劑於熱輔助法對金奈米基材之效果探討 86
4-4-1添加劑種類於熱輔助法對金奈米基材之效果 86
4-4-2 PVP濃度於熱輔助法對金奈米基材之效果 91
4-4-3 EDTA濃度於熱輔助法對金奈米基材之效果 94
4-4-4 添加劑於熱輔助法對金奈米粒子生成於ZnSe基材之元素組成探討 94
4-5 光化學輔助法與金溶液濃度對金奈米粒基材之探討 97
4-6 添加劑對於光化學輔助法對金奈米基材之效果探討 103
4-6-1 添加劑種類於光化學輔助法對金奈米基材之效果 104
4-6-2 PVP濃度於光化學輔助法對金奈米基材之效果探討 110
4-6-3 EDTA濃度於光化學輔助法對金奈米基材之效果探討 117
4-6-4 添加劑於光輔助法對金奈米粒子生成於ZnSe基材之元素組成探討 122
4-7於ZnSe表面製備金奈米SERS基材的訊號增益倍率 126
4-8 結論 128
第五章 總結 129
參考文獻 130

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