表面等离激元耦合体系及其光谱增强应用

朱旭鹏; 石惠民; 张轼; 陈智全; 郑梦洁; 王雅思; 薛书文; 张军; 段辉高

doi:10.7498/aps.68.20190782

摘要

当入射电磁波频率与金属微纳米结构中自由电子的集体振荡频率相当时, 金属微纳米结构中激发表面等离激元共振, 其共振电磁场被强束缚在亚波长尺度以下界面附近, 使其具备极大的电磁场局域能力. 这一效应可以极大程度地增强电磁波与物质的相互作用, 在金属表面等离激元耦合体系中尤为明显. 本文简述了表面等离激元耦合效应、模式耦合理论以及对应的结构耦合体系. 另外, 还介绍了一类典型耦合体系在光谱增强中的重要应用, 主要包括增强折射率传感、表面增强红外吸收、表面增强拉曼散射、表面增强光学非线性效应等.

关键词:

Abstract

Surface plasmon polariton is a surface oscillation wave that is bound at the interface between metal and dielectric material. Its oscillating electric field is strongly bound below the subwavelength scale near the interface, generating a huge enhancement of localized electromagnetic field, which can be used to greatly enhance the interaction between light and matter, particularly in metal surface plasmon coupling system. In this paper, we review the coupling effects, coupling theory, and typical coupling structures of the surface plasmon coupling systems. We also introduce a typical surface plasmon coupling system and its corresponding crucial applications in surface enhanced refractive index sensor, Raman scattering, near-infrared absorption, and nonlinear effect generation.

Keywords:

作者及机构信息

1.
岭南师范学院物理科学与技术学院, 湛江　524048

2.
广州大学机械与电气工程学院, 广州　510006

3.
湖南大学机械与运载工程学院, 长沙　410082

通信作者: 朱旭鹏, zhuxp18@lingnan.edu.cn

基金项目: 国家自然科学基金(批准号: 11574078, 61674073)、湖南省自然科学基金(批准号: 2015JJ1008, 2015RS4024)、广东省科技计划(批准号: 2017A050506056)、广东省重点基础与应用研究项目(批准号: 2016KZDXM021)、大学物理教学团队(批准号: 114961700249)和岭南师范学院自然基金(批准号: ZL1937)资助的课题.

Authors and contacts

1.
School of Physics Science and Technology, Lingnan Normal University, Zhanjiang 524048, China

2.
Center for Research on Leading Technology of Special Equipment, School of Mechanical and Electric Engineering, Guangzhou University, Guangzhou 510006, China

3.
College of Mechanical and Vehicle Engineering, State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, Hunan University, Changsha 410082, China

Corresponding author: Zhu Xu-Peng, zhuxp18@lingnan.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11574078, 61674073), the Natural Science Foundation of Hunan Province, China (Grant Nos. 2015JJ1008, 2015RS4024), the Science and Technology Planning Project of Guangdong Province, China (Grant No. 2017A050506056), the Key Basic and Applied Research Project of Guangdong Province, China (Grant No. 2016KZDXM021), the College Physics Teaching Team, China (Grant No. 114961700249), and the Foundation of Lingnan Normal University, China (Grant No. ZL1937).

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施引文献

图 1 (a)金属微纳米颗粒团聚过程^[42]; (b)不同团聚程度下的胶体颜色^[42]; (c)不同团聚程度胶体的消光光谱^[43]

Fig. 1. (a) The schematic diagram of agglomeration process when DNA molecules are added to noble metal micro-nanoparticle suspensions^[42]; (b) the color map of metal nanoparticles with different degree of agglomeration^[42]; (c) the extinction spectra of metal nanoparticles with different degree of agglomeration^[43].

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图 2 (a)银纳米粒子的原子力显微成像; (b)暗场散射成像; (c)表面增强拉曼散射谱及相应的暗场散射谱^[48]

Fig. 2. (a) The AFM image of Ag nanoparticles; (b) the dark scattering image of Ag nanoparticles; (c) the spectra of surface enhanced Raman scattering (left) and the corresponding dark scattering spectra (right). Note that the colloidal micro-nanoparticles produce a strong surface-enhanced Raman scattering with a complex scattering spectrum with multiple redshift peaks ^[48].

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图 3 (a)表面增强拉曼的金纳米颗粒热点; (b)纳米粒子的原子力显微成像; (c)纳米粒子二聚体的近场分布^[52]

Fig. 3. (a) The hotspots image of gold nanoparticles enhanced Raman scattering signal; (b) the corresponding AFM image of (a); (c) the near-field distribution when two adjacent nanoparticles are close to each other^[52].

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图 4 (a)谐振子模型^[56]; (b) LC等效电路模型^[58]; (c)模式杂化模型^[41]; (d)不同排布二聚体的模式杂化图^[39]

Fig. 4. (a) The coupling theory model of simple harmonic oscillator^[56]; (b) the LC equivalent circuit model of the surface plasmon resonance^[58]; (c) the hybrid model of surface plasmon resonance^[41]; (d) the schematic diagram of intrinsic plasmon coupling in nanorod dimer^[39].

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图 5 (a)单层纳米薄膜^[70]; (b)单个纳米星结构^[71]; (c)单个金属纳米盘及劈裂盘^[60]; (d)单个金属纳米球壳^[72]

Fig. 5. (a) The surface plasmon coupling modes and the corresponding dispersion curves in single-layer metal nanofilm^[70]; (b) the metal nanostar structure and the corresponding mode coupling process^[71]; (c) the SEM images of single metal disk and split disk with their corresponding extinction spectra^[60]; (d) the SEM images of single metal symmetric and asymmetric nanoshells with their corresponding absorption spectra during the asymmetric evolution process^[72].

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图 6 (a)三种不同厚度金属薄膜上的纳米颗粒^[72]; (b)适当距离的金属反射面上的纳米天线^[73]; (c), (d)适当距离的金属薄膜上的纳米盘^[74,75]; (e)适当距离的金属薄膜上环内纳米颗粒二聚体^[76]

Fig. 6. (a) The coupling model of three metal nano-films between the nanoparticles on film, and their corresponding absorption spectra^[72]; (b) the schematic diagram of nano-antenna radiation engineering on metal surface, its corresponding electric field distribution and sample’s SEM image^[73]; (c) the schematic diagram of nanodisk array on metal film and its corresponding SEM image^[74]; (d) the schematic diagram of metal structures on metal surface, the corresponding SEM image and the coupled electric field intensity at different wavelength^[75]; (e) the schematic diagram of the dimer structure in the ring on the metal surface, the corresponding SEM image and the local electric field distribution at resonance peak position^[76].

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图 7 (a)不对称纳米颗粒二聚体^[77]; (b)金属-介质纳米球二聚体^[78]; (c)不同特征的蝴蝶结结构^[79]; (d)同轴盘-环二聚体^[80]; (e)纵向劈裂环二聚体^[81]; (f) 不对称半环二聚体^[82]; (g)耦合的纳米线二聚体^[83]; (h) 纳米球三聚体^[84]; (i) 中心球偏离的纳米球五聚体^[85]; (j) dolmen结构^[86]; (k)纳米棒四聚体^[87]; (l)不同参数的纳米盘七聚体^[88]

Fig. 7. (a) Asymmetric nanoparticles dimer^[77]; (b) coupled heterogeneous nanoparticles^[78]; (c) symmetrical bowties^[79]; (d) concentric nanodisk-nanoring resonator^[80]; (e) split nanoring pair^[81]; (f) asymmetrical half-ring structure pair^[82]; (g) coupled nanowires^[83]; (h) nanotrimers^[84]; (i) asymmetrical nanopentamer^[85]; (j) dolmen structure^[86]; (k) nanorod tetramer^[87]; (l) nanodisk heptamers^[88]

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图 8 (a) 纳米银棒链^[89]; (b) 一维金属光栅结构^[90]; (c) 环状光栅^[91]; (d) 不对称“H”孔阵列^[92]; (e) 异心纳米盘-环谐振腔阵列^[93]; (f) THz波不对称U型环对阵列^[94]; (g) 层状负折射率结构^[95]; (h) 异质不对称“H”结构阵列^[96]

Fig. 8. (a) The SEM image and extinction spectrum of single silver nanorod chain^[89]; (b) the schematic diagram of metal one-dimensional grating structure and its corresponding transmission spectrum at TM polarization^[90]; (c) the SEM image of annular groove grating array^[91]; (d) the asymmetric compensation structures array, and the illustration is a single magnified view^[92]; (e) the SEM image of nanodisk-ring asymmetric resonator array on a conductive substrate^[93]; (f) the optical images of asymmetric U-shaped ring structure pairs array in terahertz region^[94]; (g) the layered hole array structures with a negative refractive index^[95]; (h) the heterogeneous asymmetric “H” array structures^[96].

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图 9 衬底折射率对表面等离激元模式的影响　(a)纳米球壳^[97]; (b)纳米立方体^[28]

Fig. 9. The effect of dielectric substrate on the energy of plasmon oscillation mode of nearby metal nanostructures: (a) Nanoshell^[97]; (b) nanocube^[28].

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图 10 (a)周期性纳米圆环阵列在不同折射率下的消光光谱和峰位变化^[98]; (b)金属纳米结构在不同折射率溶液中的暗场散射图^[99]; (c)金属XI结构的扫描电镜图、共振位置的电荷分布、不同环境中的消光谱^[100]; (d)太赫兹圆环缝隙阵列, 可以灵敏检测其上纳米级薄膜厚度的增加^[102]

Fig. 10. (a) The extinction spectra and peak position changes of periodic nano-ring arrays at different refractive index ^[98]; (b) the dark field scatter plot of single metal nanostructures in different refractive index solutions^[99]; (c) the SEM image of metal XI-shape structure, the new mode charge distribution formed by original mode strong coupling, and the extinction spectrum in different refractive index materials, the sensitivity of refractive index sensing can reach 1000 nm/RIU^[100]; (d) the terahertz ring-gap array for sensitive detection of the increase in nanoscale thickness of films^[102].

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图 11 (a)不同参数的金属纳米七聚体扫描电子显微图、散射光谱、表面增强拉曼谱及近场分布^[103]; (b)金膜面上半球形结构, 在结构间隙之间可以产生极大的电磁热点, 可以实现低浓度农药分子的灵敏检测^[104]; (c)动态表面增强拉曼散射检测构想, 可以解决干法检测及湿法检测灵敏性和重复性不能兼顾的难题^[105]; (d)表面增强拉曼散射探针的重要应用^[106]; (e)表面等离激元增强拉曼散射技术目前所处的现状, 瓶颈以及未来需要发展的方向^[107]

Fig. 11. (a) The SEM images of the metal nano-heptamers with different sizes, the corresponding scattering spectra, the surface enhanced Raman signal spectra and the electric field distribution^[103], the experimental results show that the strongest Raman signal can be obtained only when the coupling peak position of the heptamer is near to the peak position of the Raman shift; (b) the hemispherical structure on the gold film surface can generate a huge electromagnetic hot spot between the structure gaps, which can achieve sensitive detection of low concentration pesticide molecules^[104]; (c) the concept of dynamic surface-enhanced Raman scattering detection can solve the problem that the sensitivity and repeatability beyond the dry detection and wet detection^[105]; (d) the important applications of surface enhanced Raman scattering probes^[106]; (e) the bottlenecks and future directions surface-enhanced Raman spectroscopy^[107].

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图 12 (a)具有挂壁颗粒的垂直耦合互补天线及其在不同偏振下的电场分布和在不同间隙大小下的十八烷的手性强度^[108]; (b)金属反射面上扇形天线结构对及其不同波长下的近红外吸收增强因子^[109]; (c)不对称铝十字结构应用于红外吸收增强中的过程示意图^[110]; (d)金属共振天线应用于红外吸收增强中的过程示意图^[111]

Fig. 12. (a) Vertically coupled complementary antenna with wall particles, the corresponding electric field distribution under different polarizations and the comparisons of ODT fingerprint intensity at different gap sizes^[108]; (b) the near-infrared absorption enhancement factor of t the fan-shaped antenna with or without the reflective metal layer, when there is a reflective metal substrate, the enhancement factor can reach 10⁵ orders of magnitude^[109]; (c) the schematic diagram of applied asymmetric aluminum cross antennas to infrared absorption enhancemen^[110]; (d) the schematic diagram of metal resonant antenna applied to infrared absorption enhancement^[111].

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图 13 (a)飞秒脉冲驱动下, 银纳米棒的非线性响应示意图及其远场时间变化曲线^[112]; (b)圆柱矢量光束激发下金属微纳米低聚物中的二次谐波产生^[113]; (c)金劈裂盘在不同偏振下的散射光谱和二次谐波产生谱^[22]; (d)金矩形纳米腔阵列对四波混频的优化过程示意图^[114]; (e)用于增强非线性效应的金属纳米结构实例^[115]

Fig. 13. (a) The nonlinear response diagram of silver nanorods and its far-field temporal dynamics caves driven by femtosecond pulses^[112]; (b) second harmonic generation in metal micro-nano oligomers excited by cylindrical vector beam^[113]; (c) the SEM image of the metal split nanodisk, the corresponding dark-field scattering spectrum under different incident polarizations, the corresponding dependence between the second harmonic generation field distribution with intrinsic wavelength^[22]; (d) the schematic diagram of optimization process of four-wave mixing with gold rectangular nanocavity array^[114]; (e) examples of metal nanostructures for enhancing nonlinear effects^[115].

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图 14 (a)单颗粒及其二聚体的光致发光量子产率^[116]; (b)介质及金属上二聚体的光致发光谱^[117]; (c)金属面内二聚体天线用于荧光增强^[118]; (d)银蝴蝶结纳米结构实现对MoS₂荧光的增强^[119]; (e) WSe₂-金纳米间隙杂化结构的荧光增强图^[120]; (f)表面等离激元局域场与荧光分子团的耦合示意图^[121]; (g)表面等离激元增强荧光简图^[122]; (h)用表面等离激元纳米结构控制和增强光致发光示意图^[123]

Fig. 14. (a) Photoluminescence quantum yield of a single particle and the dimer, respectively^[116]; (b) photoluminescence spectra of nanoparticle dimer on media and metal substrate, respectively^[117]; (c) in-plane nanoantennas for fluorescence enhancement^[118]; (d) the enhanced fluorescence of MoS₂ by using silver bow nanostructures^[119]; (e) the fluorescence enhancement of WSe₂-gold plasmonic hybrid structure^[120]; (f) the schematic of a fluorophore coupled with the confined field of SPP and LSP modes, respectively^[121]; (g) cartoon of simplified plasmon enhanced fluorescence^[122]; (h) schematic illustration of controlling and enhancing PL with plasmonic nanostructures^[123].

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表面等离激元耦合体系及其光谱增强应用