介绍了一种大面积规则有序、结构可控、灵敏度高、稳定性良好、制备方法简单且易操作的表面增强拉曼散射(surface-enhanced Raman scattering, SERS) 活性基底. 以阳极氧化铝(anodic aluminum oxide, AAO) 模板一次氧化后形成的有序凹坑阵列为模板, 采用真空镀膜技术, 制备了有序的金纳米帽阵列SERS 活性基底, 并以罗丹明6G (Rhodamine 6G , R6G) 为探针分子, 测试和分析了该SERS 活性基底的表面增强拉曼光谱的特性. 结果表明, 这种SERS 活性基底对罗丹明6G 的拉曼散射信号可达到107, 具有较好的增强作用. 该纳米帽阵列结构在1 363 cm−1处的增强效果是相同厚度的普通金膜的7 倍, 且稳定性良好, 并且在放置6 个月之后, 其增强效果基本不变, 可用于化学物质和生物分子的痕量分析.
A simple and versatile method for fabricating surface-enhanced Raman scattering (SERS) active substrate with high uniformity, structural controllability, high sensitivity and great stability is reported. The ordered aluminum template formed during the synthesis of anodic aluminum oxide (AAO) film was used as the
concaved matrix. Au nanocap arrays as SERS active substrates were prepared through thermally evaporation. Taking Rhodamine 6G (R6G) as probing molecules, SERS spectra were investigated. The results indicates that these SERS active substrates displayed very strong SERS performances (Raman enhancement factor >1×107). Comparing with the ordinary Au film, the SERS enhancement effect of the Au nanocap array is about seven times stronger at 1 363 cm−1. A 6-month-old sample almost kept the same SERS activity with the newly prepared sample. Such ordered Au nanocap arrays allows application in the detection of chemical and biological molecules with trace amounts.
[1] Lin X, Cui Y, Xu Y, et al. Surface-enhanced Raman spectroscopy: substrate-related issues [J]. Analytical and Bioanalytical Chemistry, 2009, 394(7): 1729-1745.
[2] Lin X M, Cui Y, Xu Y H, et al. Surface-enhanced Raman spectroscopy: substrate-related issues [J]. Analytical and Bioanalytical Chemistry, 2009, 394(7): 1729-1745.
[3] Natan M J. Concluding remarks surface enhanced Raman scattering [J]. Faraday Discussions, 2006, 132: 321-328.
[4] Fleischmann M, Hendra P J, McQuillan A J. Raman spectra of pyridine adsorbed at a silver electrode [J]. Chemical Physics Letters, 1974, 26(2): 163-166.
[5] Chang R K, Futak T E. Surface enhanced Raman scattering [M]. New York: Plenum Press, 1982.
[6] Tian Z Q, Ren B, Wu D Y. Surface-enhanced Raman scattering: from noble to transition metals and from rough surfaces to ordered nanostructures [J]. The Journal of Physical Chemistry B, 2002, 106(37): 9463-9483.
[7] Ren B, Lin X F, Yan J W, et al. Electrochemically roughened rhodium electrode as a substrate for surface-enhanced Raman spectroscopy [J]. The Journal of Physical Chemistry B, 2003, 107(4): 899-902.
[8] Kneipp K,Wang Y, Kneipp H, et al. Single molecule detection using suface-enhanced Raman scattering (SERS) [J]. Phys Rev Lett, 1997, 78(9): 1667.
[9] Nie S, Emory S R. Probing single molecules and single nanoparticles by surface-enhanced Raman scattering [J]. Science, 1997, 275(5303): 1102.
[10] Govor L V, Bashmakov I A, Kiebooms R, et al. Self-organized networks based on conjugated polymers [J]. Advanced Materials, 2001, 13(8): 588-591.
[11] Jenekhe S A, Chen L X. Self-assembly of ordered microporous materials from rod-coil block copolymers [J]. Science, 1999, 283(5400): 372-375.
[12] Gleiche M, Chi L F, Fuchs H. Nanoscopic channel lattices with controlled anisotropic wetting [J]. Nature, 2000, 403(6766): 173-175.
[13] Austin M D, Ge H, Wu W, et al. Fabrication of 5 nm linewidth and 14 nm pitch features by nanoimprint lithography [J]. Applied Physics Letters, 2004, 84(26): 5299-5301.
[14] Chang T H P, Mankos M, Lee K Y, et al. Multiple electron-beam lithography [J]. Microelectronic Engineering, 2001, 57-58: 117-135.
[15] 姚骏恩. 纳米测量仪器和纳米加工技术[J]. 中国工程科学, 2003, 5(1): 33-37.
[16] Sunwoo L, Haiwon L, Byung-jae P, et al. Selective growth of nanometre scale structures with high resolution using thermal energy in AFM lithography [J]. Nanotechnology, 2005, 16(12): 3137-3141.
[17] Lei Y, Cai W P, Wilde G. Highly ordered nanostructures with tunable size, shape and properties: a new way to surface nano patterning with a nonlithographic method [J]. Prog Mater Sci, 2007, 52: 465-539.
[18] Lei Y, Yang S, Wu M H, et al. Surface patterning using templates: concept, properties and device applications [J]. Chem Soc Rev, 2011, 40(3): 1247-1258.
[19] Debrina J, Abhijit M, Goutam D. High Raman enhancing shape-tunable Ag nanoplates in alumina: a reliable and efficient SERS technique [J]. ACS Applied Materials and Interfaces, 2012, 4(7): 3330-3334.
[20] Ji N, Ruan W D, Li Z S, et al. A potential commercial surface-enhanced Raman scattering–active substrate: stability and usability [J]. Raman Spectroscopy, 2013, 14(1): 1-5.
[21] Mu C, Zhang J P, Xu D. Au nanoparticle arrays with tunable particle gaps by template-assisted electroless deposition for high performance surfaceenhanced Raman scattering [J]. Nanotechnology, 2010, 21(1): 015604.
[22] Duan G, Cai W, Luo Y, et al. Hierarchical surface rough ordered Au particle arrays and their surface enhanced Raman scattering [J]. Applied Physics Letters, 2006, 89(18): 181918.
