在此工作中研究了非規則性銀基板和規則結構銀基板在不同波長光線照射下 的化學反應行為，並對其效率進行測量。由表面增強拉曼光譜的比對可以確定轉 換為 DMAB 的化學反應確實發生，並且該反應發生速率會隨著光強的增強而有顯 著的提升，並且在不同基板上也會深刻影響化學反應發生速率。由三十奈米無結 構銀膜和使用聚焦離子束寫上規則結構的兩組比對之中，無結構樣品幾乎不反應 而有結構樣品發生明顯反應，可以得知表面電漿子共振機制在此化學轉換過程中 扮演的獨特重要角色。
在偵測計算生成物以及反應物的比值過程中，可以得到該反應具有一個閾值 存在的現象，在到達一定的閾值之後反應便趨緩而漸漸不再發生，該閾值的大小 由基板和光線波長以及光強所決定。在規則 170 奈米和 200 奈米照射 2700 W 紅 光的實驗中，反應物的訊號甚至幾乎完全消失，肯定了表面電漿子共振結構對化 學反應發生的貢獻。
此工作中同時利用表面電漿共振造成的拉曼訊號增強以及催化化學反應發生 的兩種作用，進行原位 In-Situ 化學反應偵測，在過程中也得到了新的資訊，在同 一機台的情況下，有時表面增強拉曼訊號明顯時化學反應並未發生，但有時在表 面增強拉曼訊號模糊時就已大略發現生成物的訊號出現，說明了兩者的發生機制 存在差異，標準的物理增強電場增加使拉曼訊號增強並不能完全解釋化學反應的 發生，也對文獻中推斷的化學反應是由於電場而發生提出疑慮，電荷移轉對於該 化學反應的進行造成的影響需要進一步被釐清。
參考文獻
1. Wu, P.C., et al., Vertical split-ring resonator based nanoplasmonic sensor. Applied Physics Letters, 2014. 105(3): p. 033105.
2. Lin, J.Y., et al., Nanopatterned Substrates Increase Surface Sensitivity for Real-Time Biosensing. The Journal of Physical Chemistry C, 2013. 117(10): p.
5286-5292.
3. Lee, K.-L., et al., Enhancing Surface Plasmon Detection Using Template-Stripped Gold Nanoslit Arrays on Plastic Films. ACS Nano, 2012. 6(4): p. 2931-2939.
4. Duyne, K.A.W.a.R.P.V., Localized Surface Plasmon Resonance Spectroscopy and Sensing. Annu. Rev. Phys. Chem, 2007. 58: p. 267-297.
5. Maier, S.A., Plasmonics: Fundamentals and Applications. 2007.
6. Bryant, M.P.a.G.W., Introduction to Metal-nanoparticle Plasmonics. Contemporary Physics, 2014. 55(4): p. 352-353.
7. 邱國斌、蔡定平, 金屬表面電漿簡介. 物理雙月刊, 2006. 28(2): p. 472-485.
8. Dong, B., et al., Substrate-, Wavelength-, and Time-Dependent Plasmon-Assisted Surface Catalysis Reaction of 4-Nitrobenzenethiol Dimerizing to p,p′
-Dimercaptoazobenzene on Au, Ag, and Cu Films. Langmuir, 2011. 27(17): p.
10677-10682.
9. Johnson, P.B. and R.W. Christy, Optical Constants of the Noble Metals. Physical Review B, 1972. 6(12): p. 4370-4379.
10. Kittel, C., Introduction to Solid State Physics, 8th Edition. 2005.
11. Mulvaney, P., Surface Plasmon Spectroscopy of Nanosized Metal Particles.
Langmuir, 1996. 12(3): p. 788-800.
12. Zeman, E.J. and G.C. Schatz, An accurate electromagnetic theory study of surface enhancement factors for silver, gold, copper, lithium, sodium, aluminum, gallium, indium, zinc, and cadmium. The Journal of Physical Chemistry, 1987. 91(3): p.
634-643.
13. Rycenga, M., et al., Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications. Chemical Reviews, 2011. 111(6): p.
3669-3712.
14. Le Ru, E.C. and P.G. Etchegoin, Principles of Surface-Enhanced Raman
Spectroscopy, in Principles of Surface-Enhanced Raman Spectroscopy, E.C.L. Ru and P.G. Etchegoin, Editors. 2009, Elsevier: Amsterdam.
15. 雷敏宏、吳紀聖, 觸媒化學概論與應用. 2014.
16. Kale, M.J., et al., Controlling Catalytic Selectivity on Metal Nanoparticles by Direct Photoexcitation of Adsorbate–Metal Bonds. Nano Letters, 2014. 14(9): p.
5405-5412.
17. Davis, M.E.D.R.J., Fundamentals of Chemical Reaction Engineering.
McGraw-Hill, Boston, 2003 edition., 2012.
18. Fujishima, A. and K. Honda, Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature, 1972. 238(5358): p. 37-38.
19. Atwater, H.A. and A. Polman, Plasmonics for improved photovoltaic devices. Nat Mater, 2010. 9(3): p. 205-213.
20. Chen, Y.L., et al. Zinc Oxide Nanorod Optical Disk Photocatalytic Reactor for Photodegradation. in Frontiers in Optics 2013. 2013. Orlando, Florida: Optical Society of America.
21. Zhang, X., et al., Plasmonic photocatalysis. Reports on Progress in Physics, 2013.
76(4): p. 046401.
22. Thuillier, G.H., M.; Labs, D.; Foujols, T.; Peetermans, W.; Gillotay, D.; Simon, P.
C.; Mandel, H., The Solar Spectral Irradiance from 200 to 2400 nm as Measured by the SOLSPEC Spectrometer from the Atlas and Eureca Missions. Solar Physics, 2003.
214(1): p. 1-22.
23. Anpo, M. and M. Takeuchi, The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. Journal of Catalysis, 2003. 216(1–2): p. 505-516.
24. Awazu, K., et al., A Plasmonic Photocatalyst Consisting of Silver Nanoparticles Embedded in Titanium Dioxide. Journal of the American Chemical Society, 2008.
130(5): p. 1676-1680.
25. Kale, M.J., T. Avanesian, and P. Christopher, Direct Photocatalysis by Plasmonic Nanostructures. ACS Catalysis, 2013. 4(1): p. 116-128.
26. Xiao, M., et al., Plasmon-enhanced chemical reactions. Journal of Materials Chemistry A, 2013. 1(19): p. 5790-5805.
27. Mukherjee, S., et al., Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H2 on Au. Nano Letters, 2012. 13(1): p. 240-247.
28. Zhang, X., et al., Plasmon-driven sequential chemical reactions in an aqueous environment. Sci. Rep., 2014. 4.
29. Xu, P., et al., Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol. Sci. Rep., 2013. 3.
30. Wang, J.L., R.A. Ando, and P.H.C. Camargo, Investigating the Plasmon-Mediated Catalytic Activity of AgAu Nanoparticles as a Function of Composition: Are Two Metals Better than One? ACS Catalysis, 2014: p. 3815-3819.
31. van Schrojenstein Lantman, E.M., et al., Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nat Nano, 2012. 7(9): p. 583-586.
32. Christopher, P., H. Xin, and S. Linic, Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. Nat Chem, 2011. 3(6): p. 467-472.
33. Chen, X., et al., Visible-Light-Driven Oxidation of Organic Contaminants in Air with Gold Nanoparticle Catalysts on Oxide Supports. Angewandte Chemie International Edition, 2008. 47(29): p. 5353-5356.
34. Liu, Z., et al., Plasmon Resonant Enhancement of Photocatalytic Water Splitting Under Visible Illumination. Nano Letters, 2011. 11(3): p. 1111-1116.
35. Wang, F., et al., Plasmonic Harvesting of Light Energy for Suzuki Coupling Reactions. Journal of the American Chemical Society, 2013. 135(15): p. 5588-5601.
36. Nishijima, Y., et al., Near-Infrared Plasmon-Assisted Water Oxidation. The Journal of Physical Chemistry Letters, 2012. 3(10): p. 1248-1252.
37. E. de Jongh, P., D. Vanmaekelbergh, and J. J. Kelly, Cu2O: a catalyst for the photochemical decomposition of water? Chemical Communications, 1999(12): p.
1069-1070.
38. Marimuthu, A., J. Zhang, and S. Linic, Tuning Selectivity in Propylene
Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State. Science, 2013. 339(6127): p. 1590-1593.
39. Manjavacas, A., et al., Plasmon-Induced Hot Carriers in Metallic Nanoparticles.
42. Brongersma, M.L., N.J. Halas, and P. Nordlander, Plasmon-induced hot carrier science and technology. Nat Nano, 2015. 10(1): p. 25-34.
43. Avanesian, T. and P. Christopher, Adsorbate Specificity in Hot Electron Driven Photochemistry on Catalytic Metal Surfaces. The Journal of Physical Chemistry C, 2014.
44. Linic, S., P. Christopher, and D.B. Ingram, Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nat Mater, 2011. 10(12): p. 911-921.
45. Sun, M. and H. Xu, A Novel Application of Plasmonics: Plasmon-Driven Surface-Catalyzed Reactions. Small, 2012. 8(18): p. 2777-2786.
46. Xu, B.-B., et al., Surface-Plasmon-Mediated Programmable Optical
Nanofabrication of an Oriented Silver Nanoplate. ACS Nano, 2014. 8(7): p. 6682-6692.
47. Kleinman, S.L., et al., Creating, characterizing, and controlling chemistry with SERS hot spots. Physical Chemistry Chemical Physics, 2013. 15(1): p. 21-36.
48. Adleman, J.R., et al., Heterogenous Catalysis Mediated by Plasmon Heating. Nano Letters, 2009. 9(12): p. 4417-4423.
49. Fang, Z., et al., Evolution of Light-Induced Vapor Generation at a
Liquid-Immersed Metallic Nanoparticle. Nano Letters, 2013. 13(4): p. 1736-1742.
50. Hogan, N.J., et al., Nanoparticles Heat through Light Localization. Nano Letters, 2014. 14(8): p. 4640-4645.
51. Neumann, O., et al., Solar Vapor Generation Enabled by Nanoparticles. ACS Nano, 2013. 7(1): p. 42-49.
52. Christopher, P., et al., Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures. Nat Mater, 2012.
11(12): p. 1044-1050.
53. Huang, Y., et al., Can p,p′-Dimercaptoazobisbenzene Be Produced from p-Aminothiophenol by Surface Photochemistry Reaction in the Junctions of a Ag Nanoparticle−Molecule−Ag (or Au) Film? The Journal of Physical Chemistry C, 2010.
114(42): p. 18263-18269.
54. Kazumasa Uetsuki, P.V., *,‡,§ Taka-aki Yano,‡ Yuika Saito,‡, Taro Ichimura,‡ and Satoshi Kawata‡, Experimental Identification of Chemical Effects in Surface Enhanced Raman Scattering of 4-Aminothiophenol. J. Phys. Chem. C, 2010. 114: p. 7515–7520.
55. CORPORATION, S.M., http://www.shibaura.co.jp/
56. 高敦科技公司, http://www.kaoduen.com.tw/.
57. Molecular Probes, I., Product Information LI Silver Enhancement Kit L-24919.
58. -, E.C.b.O.P.-O.P.L.u.C.v.W.C.,
http://commons.wikimedia.org/wiki/File:ExB_Column.jpg#/media/File:ExB_Column.jp g Focused ion beam.
59. 林智仁, 場發射式掃描式電子顯微鏡的簡介. 工業材料雜誌, 1991. 181: p.
94-99.
60. 中研院物理所, http://www.phys.sinica.edu.tw/~nanofacilities/dbfib.htm.
61. Ryan Fuierer, A.R., Procedural Operation ‘Manualette’Version 10.5. 2009.
62. OLYMPUS, http://www.olympus-ims.com/.
63. COMSOL, http://www.comsol.com/.
64. Moxfyre, b.o.w.o.U.P., wiki, Molecular energy levels and Raman effect. 2009.
65. Stiles, P.L., et al., Surface-Enhanced Raman Spectroscopy. Annual Review of Analytical Chemistry, 2008. 1(1): p. 601-626.
66. Scientific, T.F., http://www.thermoscientific.cn/product/.
67. sigmaaldrich, https://www.sigmaaldrich.com/.
68. Xie, W., B. Walkenfort, and S. Schlücker, Label-Free SERS Monitoring of Chemical Reactions Catalyzed by Small Gold Nanoparticles Using 3D Plasmonic Superstructures. Journal of the American Chemical Society, 2013. 135(5): p. 1657-1660.
69. Wang, H., et al., Plasmon-driven surface catalysis in hybridized plasmonic gap modes. Sci. Rep., 2014. 4.
70. Zhao, L.-B., et al., A DFT study on photoinduced surface catalytic coupling reactions on nanostructured silver: selective formation of azobenzene derivatives from para-substituted nitrobenzene and aniline. Physical Chemistry Chemical Physics, 2012.
14(37): p. 12919-12929.
71. Shalaev, V.M., et al., Negative index of refraction in optical metamaterials. Optics Letters, 2005. 30(24): p. 3356-3358.
72. Schott, Optical glass datasheets http://www.schott.com/.
73. Hayashi, S. and T. Konishi, Scanning Near-Field Optical Microscopic Observation of Surface-Enhanced Raman Scattering Mediated by Metallic Particle-Surface Gap Modes. Japanese Journal of Applied Physics, 2005. 44(7R): p. 5313.
74. Li, S.H.a.X., Optimal Size of Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy under Different Conditions. Journal of Nanomaterials, 2013. 2013.
75. Kim, K., et al., Surface-enhanced Raman scattering of 4,4[prime or
minute]-dimercaptoazobenzene trapped in Au nanogaps. Physical Chemistry Chemical Physics, 2012. 14(12): p. 4095-4100.
附錄
附錄一 文獻報導 PATP 的表面增強拉曼譜線位置。{Kazumasa Uetsuki, 2010 #1009}
附錄二 文獻報導 PNTP 的表面增強拉曼譜線位置。{Li, 2013 #1084}
附錄三 文獻報導 DMAB 的表面增強拉曼譜線位置。{Kim, 2012 #1008}