摘要
理想上利用奈米結構產生表面增強拉曼散射 (SERS) 應用以應用於分子檢測等，除須具備高訊號增強能力外，其結構分佈面積亦須夠大、均勻，才可達到實際應用之需求。本研究提出利用一簡單、精確且高產率之製程以製作出具有可精準控制奈米間距之雙奈米殼層金屬粒子陣列，同時具備高拉曼訊號增強效果、製造成本低、適用於水溶液環境及大面積均勻分佈等優點。
透過垂直性蒸鍍金屬層，可於雙奈米殼層金屬粒子底端產生環狀奈米間隙，大幅增加熱點分佈面積。而藉由原子層化學氣相沈積法可精確沈積僅一奈米厚之二氧化鉿層，並可有效控制雙奈米殼層金屬粒子的奈米間隙大小，使其距離縮小至五奈米以內，提供更強的耦合電場強度。透過穿透式電子顯微鏡檢視剖面可發現環狀奈米間隙之寬度隨著二氧化鉿層厚度減少而變窄，而SERS效果亦隨之增加。
本研究建構兩種金屬結構：雙奈米殼層金/金粒子及雙奈米殼層金/銀粒子，主要差別在於第二層金屬層的材料選擇。雙奈米殼層金/金粒子已提供相當高的訊號提升能力，然而當沈積銀層為第二層金屬層時，奈米殼層金/銀粒子則又能將其SERS效果大幅提高，其訊號提升倍率高達130倍，呈現完整的待測分子拉曼光譜。

Abstract
An ideal surface-enhanced Raman scattering (SERS) nanostructure for sensing and imaging applications should provide a high signal enhancement and can be obtained by easy fabrication process with large hot spot numbers/areas. In this paper, we present a simple, precise, and high-throughput technique for producing double-nanoshelled Au nanoparticles (DNS Au NPs) arrays with well-controlled nanogap of several nanometers by employing ALD HfO2 as the dielectric layer. This DNS Au NPs structure provides respectable SERS by inducing stronger plasmon electric field from the tunable nanogap structure ranging between 10 and 1 nm and large hot-spot areas as a nanoring instead of a spot. The SERS enhancement is inversely proportional to the thickness of HfO2 and a maximum of 20 folds enhancement is found at 1nm nanogap. Moreover, we also employed Ag as second layer instead of Au forming DNS Ag NPs structures, and it significant improved the SERS performance more than an order to the DNS Au NPs.

總目錄
摘要………………………………………………………………………………... i
Abstract……………………………………………………………………………. ii
致謝……………………………………………………………………………….. iii
總目錄……………..……………………………………………………………… iv
圖目錄……………………………………………………………………………. viii
表目錄……………………………………………………………………………. xi
第1章 緒論……………………………………………………………………....1
1.1 前言………………………………………………………………………1
1.2 研究動機…………………………………………………………………4
第2章 文獻回顧…………………………………………………………………5
2.1 拉曼光譜學…………………………………………………………….5
2.1.1 拉曼散射機制……………………………………………………5
2.2 表面增強拉曼散射 (SERS) ………………………………………….7
2.2.1 SERS機制………………………………………………………...9
2.3 奈米金屬粒子之SERS效應…………………………………………..12
2.2.1 粗糙表面奈米金屬粒子…………………………………………12
2.2.2 相鄰奈米間隙之奈米金屬粒子…………………………………14
2.2.3 相鄰三維奈米間隙之奈米金屬粒子…………………...………16
2.2.4 具高深寬比表面金奈米結構之聚苯乙烯奈米球……...….…...19
2.2.5 金/銀奈米粒子對之SERS效應………………...…………….…20
2.4 奈米結構製造與方法………………………………...……...…..…...21
2.4.1 微影技術………………………………………...………............21
第3章 實驗設計與規劃…………………………………………...………..……..27
3.1 實驗設計與架構……...……………………………...…….……....…27
3.1.1 奈米金粒子陣列………………………………...……………....28
3.1.2 雙奈米殼層之奈米金粒子……………………...………………30
3.1.3 雙奈米殼層之奈米金/銀粒子…………………...……...………33
3.1.4 奈米結構形貌及光學特性之檢測……………...………............34
3.2 實驗流程設計…………………….…………………...………….......34
3.2.1 奈米金球陣列製作……………………………...………...….....34
3.2.2 建構雙奈米殼層結構之奈米金/銀粒子……………………......35
3.2.3 光學特性量測…………………………………...………...….....36
3.3 實驗藥品、材料與儀器……………………………...…………........36
3.3.1 實驗檢體………………………………………….......................36
3.3.2 實驗儀器…………………………………………...…….....…..36
第4章 實驗步驟……………….…………………………………..……..….43
4.1 晶片製作…………………………………………………..………....43
4.1.1 試片清潔……………………………………………...……...…43
4.1.2 試片親水化處理……………………………………...…...........43
4.1.3 聚苯乙烯奈米球自組裝排列………………………...……...…44
4.1.4 電子束蒸鍍製程……………………………………...………...44
4.1.5 聚苯乙烯奈米球掀離………………………………..................44
4.1.6 高溫退火製程………………………………………...…...…....45
4.1.7 建構雙奈米殼層之奈米金粒子……………………...……...…45
4.1.8 建構雙奈米殼層之奈米金/銀粒子…………………...………..46
4.1.9 掃描式電子顯微鏡表面結構分析……………………...…...…46
4.1.10 穿透式電子顯微鏡剖面結構分析……………………...…...…46
4.1.11 拉曼光譜檢測分析及比較……………………………………..46
第5章 結果與討論…………………………………………………………..49
5.1 晶片製作……………………………………………………………..49
5.1.1 奈米金球陣列………………………………………..…..……..49
5.1.2 雙奈米殼層之金球…..…………………………..……..………50
5.2 R6G分子拉曼散射光檢測………………………………………….51
5.2.1 量測方式…………………………………………..……………51
5.2.2 拉曼散射光量測........................…………………..………........51
5.2.3 R6G之SERS光譜.............…………………….……….……...53
第6章 結論…………………………………………………..…………........62
第7章 未來展望……………………………………………………………..65
參考文獻……………………………………………………………..………………66

參考文獻
[1] X. Dou, Y. Yamaguchi, H. Yammamoto, S. Doi, Y. Ozaki, ”Quantitative analysis of metabolites in urine using a highly precise, compact near-infrared Raman spectrometer”, Vibrational spectroscopy, 13, 83-89, 1996
[2] J. W. McMurdy III, A. J. Berger, “Raman Spectroscopy-Based Creatinine Measurement in Urine Samples from a Multipatient Population”, Applied Spectroscopy 57, 5, 2003
[3] J. R. Baenal, B. Lendl, ” Raman spectroscopy in chemical bioanalysis ”, Current Opinion in Chemical Biology, 8, 534–539, 2004
[4] R. L. McCreery, “Raman Spectroscopy for chemical analysis”, New York: Wiley Interscience, 2000
[5] M. Fleischmann, P. J. Hendra, A. J. McQuillan, "Raman Spectra of Pyridine Adsorbed at a Silver Electrode", Chemical Physics Letters, 26, 163–166, 1974
[6] A. Campion, P. Kambhampati, “Surface-enhanced Raman scattering”, Chemical Society Reviews, 27, 241-250, 1998
[7] Y. Maruyama, M. Ishikawa, M. Futamata, “ATR-SNOM Raman Spectroscopy using Surface Plasmon Polariton”, Analytical Science, 17, 2001
[8] S. Nie, S. R. Emory, ” Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering”, Science, 275, 1997
[9] M. Moskovits, “Surface roughness and the enhanced intensity of Raman scattering by molecules adsorbed on metals”, J. Chem. Phys., 69, 1459-1461, 1978
[10] K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari and M.S. Feld, “Surface-enhanced Raman scattering and biophysics”, J. Phys.: Condens. Matter, 14, 597-624, 2002
[11] M. Moskovits, ”Surface-enhanced spectroscopy”, Reviews of modern physics, 57, 785-826, 1985
[12] W. Rechberger, A. Hohenau, A. Leitner, J. R, Krenn, B. Lamprecht, F. R. Aussenegg, ”Optical propertices of two interacting gold nanoparticles”, Optics Communications, 220, 137-141, 2003
[13] M. Kuwahara, T. Nakano, C. Mihalcea, T. Shima, J. H. Kim, J. Tominaga, and N. Atoda, “Less than 0.1um linewidth fabrication by visible light using super-resolution near-field structure” Microelectronic Engineering, 57-58, 883-890, 2011
[14] J. J. Chyou, S. J. Chen, C. S. Chu, et al., “Multi-experiment linear data analysis for ATR biosensors, “ Proc. SPIE, 2002
[15] D. K. Lim, K. S. Jeon, H. M. Kim, J. M. Nam, Y. D. Suh, “Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection”, Nature Material, 9, 2010
[16] J. Xie, Q. Zhang, J. Y. Lee, Daniel I. C. Wang, “The Synthesis of SERS-Active Gold Nanoflower Tags for In Vivo Applications ”, ACS. Nano, 2, 12, 2473-2480, 2008
[17] W. Rechberger, A. Hohenau, A. Leitner, J. R. Krenn, B. Lamprecht, F. R. Aussenegg, Opt. Commun., 220, 137-141, 2003
[18] P. K. Jain, W. Huang, M. A. El-Sayed, “On the Universal Scaling Behavior of the Distance Decay of Plasmon Coupling in Metal Nanoparticle Pairs: A Plasmon Ruler Equation”, Nano Letters, 7, 7, 2080-2088, 2007
[19] P. G. Etchegoin, E. C. Le Ru, “A perspective on single molecule SERS: current status and future challenges”, J. Phys. Chem. Chem. Phys., 10, 6079–6089, 2008
[20] E. C. Le Ru, P. G. Etchegoin and M. Meyer, J. Chem. Phys., 
125, 204701, 2006
[21] A. Cunningham, S. Mühlig, C. Rockstuhl, T. Bürgi, “Coupling of Plasmon Resonances in Tunable Layered Arrays of Gold Nanoparticles”, J. Phys. Chem. C, 115, 8955–8960, 2011
[22] G. Decher, Science, 277, 1232–1237, 1997
[23] J. Kimling, M. Maier, B. Okenve, V. Kotaidis, H. Ballot, A. Plech, J. Phys. Chem. B 110, 15700–15707, 2006
[24] H.Y. Hsieh, J. L. Xiao, C. H. Lee, T. W. Huang, C. S. Yang, P. C. Wang, F. G. Tseng, “Au-Coated Polystyrene Nanoparticles with High-Aspect-Ratio Nanocorrugations via Surface-Carboxylation-Shielded Anisotropic Etching for Significant SERS Signal Enhancement”, J. Phys. Chem. C, 115, 16258-16267, 2011
[25] C. Liusman, H. Li, G. Lu, J. Wu, F. Boey, S. Li, H. Zhang, “Surface-Enhanced Raman Scattering of Ag-Au Nanodisk Heterodimers”, J. Phys. Chem. C, 116, 10390-10395, 2012
[26] Y. Song, Y. Yang, C. J. Medforth, E. Pereira, A. K. Singh, H. Xu, Y. Jiang, C. J. Brinker, F. Swol, J. A. Shelnutt, “Controlled Synthesis of 2-D and 3-D Dendritic Platinum Nanostructures”, J. Am. Chem. Soc., 126, 635–645, 2004
[27] J. I. Martin, J. Nogues, K. Liu, J. L. Vicent, and I. K. Schuller, "Ordered magnetic nanostructures: fabrication and properties," Journal of Magnetism and Magnetic Materials, 256, 449-501, 2003
[28] G. M. Whitesides, J. C. Love, "The art of building small - Researchers are discovering cheap, efficient ways to make structures only a few billionths of a meter across," Scientific American, 285, 38-47, 2001
[29] 鄭瑞庭, 蔡宏營, 林熙翔, 蘇建彰, 陳建洋, "簡介下世代微影技術與奈米轉印微影技術", 機械工業雜誌, 245, 106-116
[30] K. Bessho, Y. Iwasaki, and S. Hashimoto, "Nanoscale magnetic mounds fabricated using a scanning probe microscope," Ieee Transactions on Magnetics, 32, 4443-4447, 1996
[31] S. Y. Chou, P. R. Krauss, and P. J. Renstrom, "Nanoimprint lithography," The Journal of Vacuum Science and Technology B, 14,4129-4133, 1996.
[32] G. Zhang, D. Y. Wang, and H. Mohwald, "Ordered binary arrays of Au nanoparticles derived from colloidal lithography," Nano Letters, 7, 127-132, 2007
[33] M. Alexe, C. Harnagea, and D. Hesse, "Non-conventional micro- and nanopatterning techniques for electroceramics," Journal of Electroceramics, 12, 69-88, 2004
[34] E. Sirotkin, J. D. Apweiler, F. Y. Ogrin, “Macroscopic Ordering of Polystyrene Carboxylate-Modified Nanospheres Self-Assembled at the Water-Air Interface”, Langmuir, 26, 13, 10677–10683, 2010
[35] Y. Song, W. A. Steen, D. Pena, Y. B. Jiang, C. J. Medforth, Q. Huo, J. L. Pincus, Y. Qiu, D. Y. Sasaki, J. E Miller, et al., “Foamlike Nanostructures Created from Dendritic Platinum Sheets on Liposomes”, Chem. Mater, 18, 2335–2346, 2006
[36] X. Teng, S. Maksimuk, S. Frommer, H. Yang, “Three- Dimensional PtRu Nanostructures” Chem. Mater. , 19, 36–41, 2007