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表面等离激元增强的光和物质相互作用

虞华康 刘伯东 吴婉玲 李志远

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表面等离激元增强的光和物质相互作用

虞华康, 刘伯东, 吴婉玲, 李志远

Surface plasmaons enhanced light-matter interactions

Yu Hua-Kang, Liu Bo-Dong, Wu Wan-Ling, Li Zhi-Yuan
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  • 表面等离激元近年来受到了广泛的关注. 得益于表面等离激元的强局域约束作用, 光场和能量被限制在亚波长尺度上, 因而各种光和物质相互作用可得到显著的增强. 表面等离激元的特性与材料、形貌、结构密切相关, 相应的共振波长可覆盖紫外、可见光、近红外到远红外的光谱波段. 由于表面等离激元的强局域电场, 光与物质的相互作用, 如荧光、拉曼散射、非线性光学、光热转换、光-声效应、催化、光伏转换等, 都得以显著增强. 本文简要回顾了表面等离激元的物理特性, 具体讨论了各种基于表面等离激元增强的光和物质相互作用机理及相关应用, 并探讨了存在的问题和进一步发展的方向. 本文旨在为构造更高性能的表面等离激元器件, 发展相关技术, 进一步拓展表面等离激元的应用领域提供有益的参考.
    Surface plasmon polaritons (SPPs) have been widely investigated in the past decades. Due to their unique feature of field localization, optical energy can be strongly confined in the subwavelength and even nanoscale space. This strong confinement gives rise to dramatically increased electromagnetic field strength, leading to greatly enhanced light-matter interactions. The properties of SPP are strongly dependent on material, morphology and structure. The wavelength of surface plasmon resonance can be readily manipulated over broadband optical spectra, covering ultraviolet, visible, near infrared to far infrared. In this review article, both working principle and applications of surface plasmon enhanced light-matter interactions, such as fluorescence, Raman scattering, nonlinear optics, heat effects, photoacoustic effects, photo-catalysis, and photovoltaic conversion, are comprehensively reviewed. Besides, the current problems and future research directions of surface plasmons are discussed. Our paper provides valuable reference for future high-performance plasmonic device and technology applications.
      通信作者: 李志远, phzyli@scut.edu.cn
    • 基金项目: 国家重点研发计划(批准号: 2018YFA0306200)、国家自然科学基金(批准号: 1434017, 11604230, 91850107)和广东省创新创业研究团队项目(批准号: 2016ZT06C594)资助的课题.
      Corresponding author: Li Zhi-Yuan, phzyli@scut.edu.cn
    • Funds: Project supported by the National Key R&D Program of China (Grant No. 2018YFA0306200), the National Natural Science Foundation of China (Grant Nos. 511434017, 11604230, 91850107), and the Innovative and Entrepreneurial Research Team Program of Guangdong Province, China (Grant No. 2016ZT06C594).
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  • 图 1  LSPP和PSPP的物理性质 (a) 在入射光的电场作用下金属纳米颗粒表面等离激元振荡示意图, 显示了自由电子气团在外界光场的电场作用下产生相对于核心的位移, 激发了LSPP; (b) 电场作用下金属-电介质界面表面等离子体振荡示意图, 显示了PSPP被外界光场所激发, 在金属和电介质内部电场均可以被局域亚波长尺度内; (c) 金纳米棒的吸收光谱, 显示出存在着横向共振(短波)和径向共振(长波)两个LSPP共振峰; (d) 金属-电介质界面PSPP的色散关系(实线), 同时显示真空中光色散关系(虚线)

    Fig. 1.  Basic physical properties of LSPP and PSPP: (a) Oscillation of free electrons in metal nanoparticle with respect to the particle center when driven by the electric field of incident light, indicating ignition of surface plasmon resonance and excitation of LSPP; (b) surface charge (minus electrons and positive ions) oscillation with respect to each other at the metal-dielectric interface when driven by the electric field of TM-polarized incident light, indicating the excitation of PSPP and the subwavelength localization of electric field around the interface; (c) absorption spectrum of gold nanorod, indicating the existence of short-wavelength transverse LSPP and long- wavelength longitudinal LSPP mode simultaneously in this nanoparticle system; (d) the dispersion curve for a PSPP mode at the metal-dielectric interface (solid curve) together with the dispersion of light in vacuum (dashed curve).

    图 2  银纳米颗粒在紫外波段的消光光谱(黑线)、吸收光谱(红线)和散射光谱(蓝线) (a) 球体; (b) 立方体; (c) 四面体; (d) 正八面体; (e) 空心球体(壳厚度为10 nm); (f) 薄球壳(壳厚度为5 nm)[14]

    Fig. 2.  Calculated UV−vis extinction (black), absorption (red), and scattering (blue) spectra of silver nanostructures: (a) Anisotropic sphere; (b) anisotropic cubes; (c) tetrahedra; (d) octahedra; (e) hollow sphere (with 10 nm shell); (f) thinner shell walls (with 5 nm shell) (Fig. 2 adapted from Ref. [14] with permission)

    图 3  (a) 在Si3N4薄膜上, 呈蝴蝶结型的纳米颗粒结构的扫描电子显微镜(SEM)照片, 几个蝴蝶结的间隙大小不一样; 用时域有限差分方法计算得到的(b) 785 nm和(c) 632.8 nm两种激光照射时, 间隙为6 nm的蝴蝶结型金纳米结构上的电场强度(${\left| E \right|^2}$)分布; (d) 海胆型纳米颗粒的SEM照片; (e) 633 nm激光照射时, 海胆型纳米颗粒在轴面上的电场强度(${\left| E \right|^2}$)分布. 图(a)−(c)来源于文献[17]; 图(d)−(e)来源于文献[18]

    Fig. 3.  (a) The SEM image of bowtie nanoantenna exposed on the Si3N4 membrane with varied gap sizes in the range of 3 to 24 nm; the FDTD calculated electric field intensity, ${\left| E \right|^2}$, of the gold bowtie nanoantenna with 6 nm gap at an excitation wavelength of (b) 785 nm and (c) 632.8 nm; (d) the SEM image of a sea urchin-like nanoparticle with an external diameter of 400 nm; (e) the typical distributions of the electric field strength (${\left| E \right|^2}$) calculated in a plane across a vertical axis of particles irradiated at 633 nm(Fig. 3(a)-(c) adapted from Ref. [17] and (d)−(e) adapted from Ref. [18] with permission).

    图 4  (a) 银纳米棒的SEM照片; (b) 纳米棒在可见光-近红外波段的消光光谱[27]

    Fig. 4.  (a) The SEM image of silver nanobars; (b) the Vis-NIR extinction spectrum of nanobars (Fig. 4 adapted from Ref. [27] with permission).

    图 5  (a) 不同长径比的纳米棒的SEM照片, 及其相应的归一化散射光谱; (b) 宽度、高度均保持50 nm不变, 长度分别为100, 150和200 nm的纳米棒, 用DDA方法计算得的散射光谱[27]

    Fig. 5.  (a) The SEM images of individual nanobars and the corresponding normalized scattering spectra; (b) DDA calculated scattering spectra of nanobars with varied lengths in 100, 150, and 200 nm, keeping width in 55 nm and height in 50 nm (Fig. 5 adapted from Ref. [27] with permission).

    图 6  用经典理论分析拉曼散射的(a) 激发过程和(b) 辐射过程; 用多重瑞利散射效应分析拉曼散射的(c) 激发过程和(d) 辐射过程[48]

    Fig. 6.  (a) The excitation process and (b) the radiation process of normal spontaneous Raman enhancement; (d) the excitation process and (d) the radiation process of spontaneous Raman enhancement (Fig. 6 adapted from Ref. [48] with permission).

    图 7  活癌细胞成像的(a) 亮视场、(b) 荧光显微成像图; (c) 无金纳米颗粒的成像对比图; (d)−(f) 基于特殊金纳米颗粒的癌细胞成像及相应的放大图像, 可以看出光声信号对比度很高, 足以识别出单个癌细胞, 如虚线圆圈所示[105]

    Fig. 7.  (a) Bright-field and (b) fluorescence microscopic imaging of single live cancer cells; (c) control image shows no obvious photoacoustic signals for cancer cell not treated with gold nanoparticles; (d)−(f) typical images and corresponding enlarged images for cells treated with gold nanoparticles, showing photoacoustic signals strong enough to identify single cancer cells in dashed circles (Fig. 7 adapted from Ref. [105] with permission).

    图 8  表面等离激元光学的研究现状和进一步发展的展望分析路线图

    Fig. 8.  Analysis and roadmap for the current state and future development perspective of plasmonics.

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  • 收稿日期:  2019-03-09
  • 修回日期:  2019-04-10
  • 上网日期:  2019-07-01
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