MoS<sub>2</sub>及其金属复合表面增强拉曼散射基底的发展及应用

李金华; 张思楠; 翟英娇; 马剑刚; 房文汇; 张昱

doi:10.7498/aps.68.20182113

摘要

表面增强拉曼散射(surface enhanced Raman spectroscopy, SERS)作为一种超灵敏的无标签分析技术, 在分子检测领域得到了广泛的研究及发展, 而增强机理的探究及灵敏度、均匀性、稳定性等性能的提升一直是研究人员面临的重要挑战. 本文通过梳理SERS机理的国内外研究进展, 综述了单一金属基底、二硫化钼(MoS₂)基底及金属/MoS₂复合基底的机理及研究现状和存在的问题等; 总结介绍了二硫化钼基底及金属/二硫化钼复合基底制备方法的优缺点; 概述了二硫化钼及其金属复合基底在食品检测、生物医学、环境污染监测等方面的应用研究进展; 最后提出了SERS技术目前存在的不足并对其发展前景进行了展望.

关键词:

Abstract

Surface-enhanced Raman scattering is an ultra-sensitive molecular detection technology, and the exploration of its mechanism and the improvement of sensitivity, uniformity and stability have always been significant challenge to researchers. In this paper, the development of surface-enhanced Raman scattering mechanism and its research progress, and thus review the mechanism, research status and existing problems of single metal substrate, molybdenum disulfide substrate and metal/molybdenum disulfide composite substrate are summarized; The preparation method of the molybdenum disulfide substrate including hydrothermal/solvothermal method, micromechanical peeling method, chemical meteorological deposition method, and preparation method of metal/molybdenum disulfide composite substrate are briefly introduced, in which the electrochemical method, thermal reduction method, seed-mediated growth method, and electron beam lithography method are covered, and the advantages and disadvantages of the above preparation methods are evaluated; The research progress of the applications of molybdenum disulfide and its metal composite substrates in food testing, biomedicine, environmental pollution monitoring, etc. are briefly overviewed The surface-enhanced Raman scattering study is extended to other transition metal binary compounds and their metal composite structures. Therefore, the metal/molybdenum disulfide composite substrate expands the types of surface-enhanced Raman scattering substrates, thereby making up for the deficiency of low reproducibility, poor stability, and weak adsorption. Moreover, it has the advantages of fluorescence quenching effect, high sensitivity, wide detection range, and it can be combined with on-site rapid separation technology, and thus has widespread application prospects. Finally, the shortcomings of surface-enhanced Raman scattering technology and prospects for its development are also pointed out.

Keywords:

作者及机构信息

1.
长春理工大学, 吉林省纳米光子学与生物光子学重点实验室, 国际纳米光子学与生物光子学联合研究中心, 长春　130022

2.
东北师范大学, 紫外光发射材料与技术教育部重点实验室, 长春　130000

通信作者: 翟英娇, zhaiyingjiao0613@cust.edu.cn

基金项目: 教育部“111”创新引智项目(批准号: D17017)、国家自然科学基金资助项目(批准号: 21703017, 11604024)、装备预研基金重点项目(批准号: 6140414020102)、吉林省科技发展计划项目(批准号: 20180519017JH)、吉林省教育厅项目(批准号: JJKH20170611KJ, JJKH20181101KJ, JJKH20181106KJ)、长春理工大学科技创新基金(批准号: XQNJJ-2016-14)和紫外光发射材料与技术教育部重点实验室开放课题资助的课题.

Authors and contacts

1.
International Joint Research Center for Nanophotonics and Biophotonics, Jilin Key Laboratory of Nanophotonics and Biophotonics, Changchun University of Science and Technology, Changchun 130022, China

2.
Key Laboratory of Ultraviolet Emitting Materials and Technology, Minstry of Education, Northeast Normal University, Changchun 130000, China

Corresponding author: Zhai Ying-Jiao, zhaiyingjiao0613@cust.edu.cn

Funds: Project supported by the “111” Innovation and Intelligence Initiation Project of Ministry of Education of China (Grant No. D17017), the National Natural Science Foundation of China (Grant Nos. 21703017, 11604024), the Advance Recearch Project of Equipment (Grant No. 6140414020102), the Developing Project of Science and Technology of Jilin Province (Grant No. 20180519017JH), the Project of Education Department of Jilin Province (Grant Nos. JJKH20170611KJ, JJKH20181101KJ, JJKH20181106KJ), Science Foundation for Young Scientists of Changchun University of Science and Technology (Grant No. XQNJJ-2016-14), and Open Research Fund of Key laboratory of UV-Emitting Materials and Technology.

文章全文 : translate this paragraph

参考文献

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施引文献

图 1 金属、MoS₂、金属/MoS₂ SERS基底

Fig. 1. Metal, MoS₂, metal/MoS₂ SERS substrate.

下载: 全尺寸图片幻灯片

图 2 金属纳米球的局域表面等粒子共振示意图^[22]

Fig. 2. Schematic diagram of local surface isopoly resonance of metal nanospheres^[22]

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图 3 (a) Au矩形阵列SERS基底对R6G的SERS检测^[27]; (b) Au纳米粒子、纳米圆环阵列基底对4-MBA的SERS检测^[29]

Fig. 3. (a) SERS detection of R6G by Au rectangular array SERS substrate^[27]; (b) SERS detection of 4-MBA by Au nanoparticles and nanoring array substrates^[29]

下载: 全尺寸图片幻灯片

图 4 (a)单层MoS₂基底检测R6G流程图及SERS光谱^[34]; (b)单层MoS₂基底对4-巯基吡啶的SERS检测^[35]

Fig. 4. (a) Flow chart and SERS spectra of single-layer MoS₂ substrate for detecting R6G^[34]; (b) SERS detection of 4-mercaptopyridine by single-layer MoS₂ substrate^[35]

下载: 全尺寸图片幻灯片

图 5 Ag/MoS₂纳米花复合SERS基底机理分析示意图^[37]

Fig. 5. Analysis schematic diagram of Ag/MoS₂ nanoflower SERS substrate mechanism^[37]

下载: 全尺寸图片幻灯片

图 6 Au/MoS₂复合SERS基底的费米能级移动示意图^[39]

Fig. 6. Schematic diagram of Fermi level moving of Au/MoS₂ composite SERS substrate^[39]

下载: 全尺寸图片幻灯片

图 7 (a)卷轴形貌的Au/MoS₂、Ag/MoS₂复合基底增强拉曼强度比^[41]; (b) Cu/MoS₂复合基底、Cu基底对R6G的SERS检测^[43]

Fig. 7. (a) Reinforced Raman intensity ratio of Au/MoS₂, Ag/MoS₂ composite substrate with reel profile^[41]; (b) SERS detection of R6G by Cu/MoS₂ composite substrate and Cu substrate^[43]

下载: 全尺寸图片幻灯片

图 8 化学气相沉积法制备的金字塔形MoS₂薄膜SERS基底^[47]

Fig. 8. Pyramid-shaped MoS₂ film SERS substrate prepared by chemical vapor deposition^[47]

下载: 全尺寸图片幻灯片

图 9 电子束光刻法制备的Au领结/MoS₂复合SERS基底　(a)^[51], Au矩形/MoS₂复合SERS基底^[49] (b)和Au圆盘/MoS₂复合SERS基底(c)^[50]

Fig. 9. Au bow tie/MoS₂ composite SERS substrate prepared by electron beam lithography(a)^[51], Au rectangular/MoS₂ composite SERS substrate prepared by electron beam lithography(b)^[49] and Au disc/MoS₂ composite SERS substrate prepared by electron beam lithography(c)^[50]

下载: 全尺寸图片幻灯片

图 10 金字塔形Au-Ag/MoS₂复合SERS基底检测三聚氰胺^[52]

Fig. 10. Detection of melamine by pyramidal Au-Ag/MoS₂ composite SERS substrate.^[52]

下载: 全尺寸图片幻灯片

图 11 Au/MoS₂作为SERS基底检测水中分离出的CV和TB分子^[55]

Fig. 11. Au/MoS₂ as SERS substrate for the detection of CV and TB molecules isolated from water^[55]

下载: 全尺寸图片幻灯片

map

[1]	Howard M W, Cooney R P, Mcquillan A J 2010 J. Raman Spectrosc. 9 273
[2]	Hubbell J A, Chilkoti A 2012 Science 337 303 Google Scholar
[3]	Jin I L, Lee W K 2015 Materials Lett. 160 139 Google Scholar
[4]	Mulvihill M J, Ling X Y, Henzie J, Yang P 2010 J. Am. Chem. Soc. 132 268 Google Scholar
[5]	Otto A 2005 J. Raman Spectrosc. 36 497 Google Scholar
[6]	Sun Y, Wiederrecht G P 2007 Small 3 1825 Google Scholar
[7]	Willets K A, Van Duyne R P 2007 Annu. Rev. Phys. Chem. 58 267 Google Scholar
[8]	Popp J, Mayerhöfer T 2009 Annu. Rev. Anal. Chem. 394 1717
[9]	Conley H, Wang B, Ziegler J I, Haglund R F, Pantelides S T, Bolotin K I 2013 Nano Lett. 13 3626 Google Scholar
[10]	Li X, Li J, Wang X, Hu J, Fang X, Chu X, Wei Z, Shan J, Ding X 2014 Integ. Ferroelectr. 158 26 Google Scholar
[11]	Li J, Li X, Wang X, Hu J, Chu X, Fang X, Wei Z 2016 Surf. Eng. 32 245 Google Scholar
[12]	Zhai Y, Li J, Chu X, Xu M, Jin F, Li X, Fang X, Wei Z, Wang X 2016 J. Alloy. Compd. 672 600 Google Scholar
[13]	Zhai Y, Li J, Chu X, Xu M, Jin F, Fang X 2016 IEEE International Conference on Manipulation, Manufacturing and Measurement on the Nanoscale (3M-NANO) Chongqing, China, July 18-22, p287s
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[18]	Fears R, Gehr P 2012 Nature 488 281
[19]	Singh R 2002 Phys. Perspect. 4 399 Google Scholar
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[21]	Albrecht M G, Creighton J A 1977 J. Am. Chem. Soc. 99 5215 Google Scholar
[22]	Banholzer M J, Millstone J E, Qin L, Mirkin C K A 2008 Chem. Soc. Rev. 37 885 Google Scholar
[23]	Khlebtsov B N, Khlebtsov N G 2007 J. Phys. Chem. C 111 11516
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[27]	Zhang P, Yang S, Wang L, Zhao J, Zhu Z, Liu B, Zhong J, Sun X 2014 Nanotechnology 25 245301 Google Scholar
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[29]	Wu T, Lin Y W 2018 Appl. Surf. Sci. 435 1143 Google Scholar
[30]	Tian Z Q, Ren B, Wu D Y 2002 J. Phys. Chem. B 106 9463
[31]	Moskovits M 1985 Rev. Mod. Phys. 57 783 Google Scholar
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[34]	Zang X, Yao K, Yan A 2017 International Conference on Solid-State Sensors, Actuators and Microsystems (Transducers) Taiwan, China, June 18-22, 2017 p894
[35]	Muehlethaler C, Considine C R, Menon V, Lin W C, Lee Y H, Lombardi J R 2016 Acs Photonics 3 1164 Google Scholar
[36]	Xia M 2016 Ph. D. Dissertation(California: University of California)
[37]	Liang X, Wang Y S, You T T, Zhang X J, Yang N, Wang G S, Yin P G 2017 Nanoscale 9 8879 Google Scholar
[38]	Shakya J, Patel A S, Singh F, Mohanty T 2016 Appl. Phys. Lett. 108 013103 Google Scholar
[39]	Bhanu U, Islam M R, Tetard L, Khondaker S I 2014 Sci. Rep. 4 5575
[40]	Lu J, Lu J H, Liu H, Liu B, Gong L, Tok E S, Loh K P, Sow C H 2015 Small 11 1792 Google Scholar
[41]	Hwang D Y, Suh D H 2017 Nanotechnology 28 025603 Google Scholar
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[43]	Li Z, Jiang S, Xu S, Zhang C, Qiu H, Li C, Sheng Y, Huo Y, Yang C, Man B 2016 Sensor. Actuat. B-Chem. 230 645 Google Scholar
[44]	Singha S S, Mondal S, Bhattacharya T S, Das L, Sen K, Satpati B, Das K, Singha A 2018 Biosens. Bioelectron. 119 10 Google Scholar
[45]	Fei X, Liu Z, Hou Y, Li Y, Yang G, Su C, Wang Z, Zhong H, Zhuang Z, Guo Z 2017 Materials 10 650 Google Scholar
[46]	Yan D, Qiu W, Chen X, Liu L, Lai Y, Meng Z, Song J, Liu X Y, Zhan D 2018 Phys. Chem. C 122 14467 Google Scholar
[47]	Qiu H, Li Z, Gao S, Chen P, Zhang C, Jiang S, Xu S, Yang C, Li H 2015 Rsc Adv. 5 83899 Google Scholar
[48]	夏洪坤, 邹利锋, 马楠, 嵇天浩 2016 人工晶体学报 45 291 Google Scholar Xia H K, Zou L F, Ma N, Ji T H 2016 J. Synthetic Cryst. 45 291 Google Scholar
[49]	Najmaei S, Mlayah A, Arbouet A, Girard C, Léotin J, Lou J 2014 Acs Nano 8 12682 Google Scholar
[50]	Butun S, Tongay S, Aydin K 2015 Nano Lett. 15 2700 Google Scholar
[51]	Lee B, Park J, Han G H, Ee H S, Naylor C H, Liu W, Johnson A T, Agarwal R 2015 Nano Lett. 15 3646 Google Scholar
[52]	Xu J, Li C, Si H, Zhao X, Wang L, Jiang S, Wei D, Yu J, Xiu X, Zhang C 2018 Opt. Express 26 21546 Google Scholar
[53]	Liang X, Zhang X J, You T T, Yang N, Wang G S, Yin P G 2017 J. Raman Spectrosc. 49 245
[54]	Jin K, Xie L, Tian Y, Liu D 2016 J. Phys. Chem. C 120 11204 Google Scholar
[55]	Zhao Y, Pan X, Zhang L, Xu Y, Li C, Wang J, Ou J, Xiu X, Man B, Yang C 2017 Rsc Adv. 7 36516 Google Scholar
[56]	Kim J Y, Kim J, Joo J 2016 Opt. Express 24 27546 Google Scholar
[57]	Lu Z, Si H, Li Z, Yu J, Liu Y, Feng D, Zhang C, Yang W, Man B, Jiang S 2018 Opt. Express 26 21626 Google Scholar
[58]	Nair R, Gummaluri V S, Gayathri P K, Vijayan C 2017 Mater. Res. Express 4 015025 Google Scholar

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MoS₂及其金属复合表面增强拉曼散射基底的发展及应用