手性等离激元纳米晶制备技术的研究进展

生命体中大部分生物分子都具有手性。生物分子的手性构象与等离激元纳米晶的局域表面等离激元共振(LSPR)通过偶极子-偶极子耦合作用,在其LSPR的位置会诱导出一个新的圆二色吸收光谱,具有这种光学活性的等离激元纳米晶称为手性等离激元纳米晶。手性等离激元纳米晶的光学响应信号的稳定性和可重复性都比较高,广泛应用在生物传感、化学传感、圆偏振器、光催化、癌症治疗等领域。手性等离激元纳米晶的制备技术一直是该领域的研究热点。然而,通过将手性分子直接吸附在等离激元纳米晶表面的方式所诱导的手性光学响应信号非常弱,故本综述聚焦于手性等离激元纳米晶的其他制备技术,包括通过手性分子或者软模板组装技术获得手性等离激元超结构;湿化学法将手性分子嵌入到单个纳米晶当中制备出核-壳型手性等离激元纳米晶,或者将手性分子的手性构象传递到无机纳米材料的结构当中制备出单个螺旋型手性等离激元纳米晶等。基于目前对手性等离激元纳米晶的最新研究进展,对其纳米制备技术作了进一步的总结和展望。     

石墨烯覆盖铝纳米光栅表面等离激元共振光谱及传感特性

表面等离激元共振技术具有无需标记、灵敏度高、实时检测等优点,已广泛应用于生物医疗、环境监测及食品安全等领域。相对于传统贵金属材料表面等离激元共振传感器而言,铝表面等离激元共振传感器具有价格低廉、共振光谱带宽小等优点,已逐渐成为了该领域的研究热点。针对铝材料存在与生物分子兼容性差、易氧化等缺点,利用石墨烯化学稳定性好、比表面积大、抗氧化能力强、生物兼容性好等独特优势,将其作为与被测分子直接接触的传感层,提出了一种石墨烯覆盖铝纳米光栅的表面等离激元共振传感器。首先,基于多物理场有限元仿真软件建立了该传感器的物理模型,分别分析了石墨烯层数和铝光栅结构参数(占空比、高度、周期)对传感器共振光谱的影响。结果表明,石墨烯与铝光栅的复合有效增强了入射光波与传感器的相互作用,采用单层石墨烯与铝光栅复合时,共振峰具有最窄的光谱带宽。当铝纳米光栅结构Λ=600 nm,H=40 nm,η=70%时,光谱反射率为零。进一步分析了结构优化后的传感器的传感特性。结果表明,单层石墨烯覆盖铝纳米光栅传感器具有最高的品质因数24.5 RIU-1,其灵敏度高达626 nm·RIU-1。该传感器具有探测精度高、分子兼容性好等优点,能为生化分析、环境监测和食品安全等领域提供一个新的绿色传感平台。     

基于人工局域表面等离激元的高灵敏传感研究进展（特邀）

人工局域表面等离激元是一种基于表面等离激元超材料的电磁谐振模式，在微波、毫米波和太赫兹频段可实现深亚波长场束缚、高品质因子、高介电灵敏度等优异传感特性，并且与平面印刷电路工艺兼容，易于和信号检测电路、无线通信电路集成，因此在小型化便携式的物联传感领域展现出广阔的应用前景。本文重点介绍人工局域表面等离激元传感的新原理、相关技术及典型应用。在传感新原理方面，讨论了新型人工局域表面等离激元的谐振结构、电磁模式、以及涡旋波传感原理；在传感指标提升技术方面，探讨了模式间耦合和有源放大两种传感增强方法；在应用探索方面，回顾了人工局域表面等离激元在溶液浓度传感、细胞传感和力学量传感等方向的代表性工作，介绍了小型化人工局域表面等离激元传感系统的最新进展。最后，对人工局域表面等离激元传感的发展趋势进行了讨论和展望。     

表面等离激元纳米阵列结构传感器的集成化和小型化研究

表面等离激元由于其异常的光学特性在高灵敏度传感领域有着广泛的应用前景。然而,传统棱镜式表面等离激元传感器由于庞大的体积和昂贵的成本限制了其进一步发展。表面等离激元金属纳米阵列结构传感器的出现为实现低成本、小型化和集成化的表面等离激元传感器提供了一条有效的解决途径。文章首先总结了表面等离激元纳米阵列结构传感器的发展现状和应用优势,然后主要介绍了近期作者课题组在表面等离激元传感器小型化、集成化、低成本方面的一些工作。这些工作对推动表面等离激元传感理论的发展,实现金属纳米阵列传感技术器件化具有较为重要的现实意义。     

基于棱镜型消逝场耦合增强拉曼/荧光原位光谱检测系统

为解决单一技术在表界面过程研究中的局限性,发展多技术协同配合的综合探测装置具有重要意义。该研究使用Kretschmann棱镜激发银膜表面等离激元极化子(SPP),并在银膜表面修饰具有拉曼及荧光活性的目标分子。利用分子对表面电磁场的散射和吸收,将近场的能量重新发射到远场,实现探测。基于该技术,搭建了一套原位融合表面等离激元共振(SPR)光谱、表面增强拉曼散射(SERS)、表面等离激元增强荧光的检测系统,用于实现高灵敏的表界面事件监控及光谱分析功能,并以Cy5.5@SiO₂@AuNP@4MBA荧光拉曼双探针为标准样品对仪器功能进行验证。该装置在动态调控等离激元器件,生物传感与检测,界面光电催化等领域均有很多潜在应用。     

表面等离激元耦合体系及其光谱增强应用

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.     

基于COMSOL Multiphysics对Cu2S量子点的表面等离激元共振模拟研究

Cu₂S量子点作为一种新型半导体纳米材料以其特有的化学及光学性质而越来越被人们所关注. 本文通过应用COMSOL Multiphysics4.2a这一基于有限元法的模拟软件, 运用其中的电磁波模块, 结合Maxwell电磁波理论对影响Cu₂S量子点产生表 面等离激元共振的条件做出了模拟分析, 运用Kretschmann棱镜耦合系统建立了理论模型, 通过改变量子点的粒径、有机溶剂的折射率、入射光的波长以及对量子点进行包裹等方式, 模拟出在不同条件下Cu₂S量子点产生表面等离激元共振信号的情况, 为Cu₂S量子点在表面等离激元共振传感中的实际应用提供了理论依据和参考. 关键词： COMSOL Multiphysics 2S量子点')" href="#">Cu₂S量子点 表面等离激元共振 有限元法     

表面等离极化激元的散射及波前调控

表面等离极化激元在片上信号传输、增强非线性/拉曼效应、生物/化学传感、超分辨成像等方面具有重要应用.在这些应用中,表面等离极化激元的近场传输及远场散射起着重要作用.然而,长期以来人们对相关物理效应缺乏简单有效的理论理解,这也限制了人们对表面等离极化激元的自由调控.本文首先简单回顾了表面等离极化激元的发展历史及现状,接着着重介绍了表面等离极化激元的近场传输效应和远场散射效应,包括其理论进展及其相关应用;最后还介绍了表面等离极化激元的近场波前调控的相关方法.基于这些进展,人们对表面等离极化激元的散射特性有了更为深刻的理解和更加强大的调控能力,这将对未来表面等离极化激元相关研究和应用带来启发.     

局域表面等离激元

局域表面等离激元使得贵金属纳米颗粒具有丰富的光学性质,其应用涵盖能源、生物医学、安全、信息、超材料等诸多领域。文章简要介绍局域表面等离激元的基本性质、贵金属纳米结构中的局域表面等离激元共振耦合以及具有局域表面等离激元特性的贵金属纳米结构的一些重要应用。     

柱状磁光颗粒的局域表面等离激元共振及尺寸效应

柱状磁光颗粒的局域表面等离激元共振为二维磁光光子晶体的手征性边缘模的生成提供了重要的机制. 但目前对此类颗粒的局域表面等离激元共振效应的研究局限于长波长近似下的结果, 且缺乏对发生共振时的远场与近场特征的深入了解. 本文从散射理论出发, 计算并分析了柱状磁光颗粒发生局域表面等离激元共振的条件与特殊的场特征, 并讨论了颗粒尺寸对共振峰的影响. 计算结果解释了实验中观察到的二维磁光光子晶体的共振带隙与在长波长近似下得到的局域表面等离激元共振频率的明显偏移, 并展示了颗粒在较大尺寸下形成的高阶共振峰, 这可能有助于利用共振效应在磁光光子晶体中实现多模的手征边缘态.     

Design optimization of highly sensitive LSPR enhanced surface plasmon resonance biosensors with nanoholes

For breaking through the sensitivity limitation of conventional surface plasmon resonance (SPR) biosensors, novel highly sensitive SPR biosensors with Au nanoparticles and nanogratings enhancement have been proposed recently.But in practice, these structures have obvious disadvantages.In this study, a nanohole based sensitivity enhancement SPR biosensor is proposed and the influence of different structural parameters on the performance is investigated by using rigorous coupled wave analysis (RCWA).Electromagnetic field distributions around the nanohole are also given out to directly explain the performance difference for various structural parameters.The results indicate that significant sensitivity increase is associated with localized surface plasmons (LSPs) excitation mediated by nanoholes.Except to outcome the weakness of other LSP based biosensors, larger resonance angle shift, reflectance amplitude, and sharper SPR curves' width are obtained simultaneously under optimized structural parameters.     

Investigation of the sensitivity of H-shaped nano-grating surface plasmon resonance biosensors using rigorous coupled wave analysis

The sensitivity of an angle-resolved surface plasmon resonance biosensor is not only determined by the shift of the resonance angle, but also the width of the SPR curves and reflective amplitude. The three factors should be considered simultaneously in designing a SPR biosensor. In this study, a H-shaped nano-grating-based SPR biosensor is proposed and the influence of different structural parameters on the performance is investigated by using rigorous coupled wave analysis (RCWA). Electric field distribution around the nano-grating are also given out to directly explain the performance difference for various structural parameters. Larger resonance angle shift, reflectance amplitude and sharper SPR curves’ width are obtained simultaneously under optimized structural parameters. Our study is usefully for understanding of the enhancement mechanism of the nano-grating SPR biosensor and also provides instructions for fabricating highly sensitive SPR biosensors. PACS 42.79.Dj; 42.81.Gs; 73.20.Mf; 07.07.Df     

Optical biosensor with dispersion compensation

Dispersion limits performance in many optical systems. In surface plasmon resonance (SPR) biosensors, the sensing area is an optical element in which the dispersion depends on the effective refractive index of the biochemical compounds to be measured. We report a method of compensating for wavelength dispersion in SPR biosensors employing two integrated diffractive optical coupling elements in a polymer substrate. The dispersion compensation is achieved over the whole dynamic measurement range and provides a biosensor more robust to wavelength fluctuations than prism-coupler SPR systems. The concept can readily be employed in other types of sensor measuring refractive-index changes.     

Enhancement of the resolution of surface plasmon resonance biosensors by control of the size and distribution of nanoparticles

A new resolution-enhanced surface plasmon resonance (SPR) biosensor offers a tenfold improvement in resolution compared with conventional SPR biosensors in the detection of the surface coverage of biomaterials. The proposed optical biosensor, based on the attenuated total-reflection method, excites both the surface plasmons and particle plasmons to enhance the local electromagnetic field by control of the size and volume fraction of embedded Au nanoparticles to increase the resolution of the device. The SPR biosensor design is based on the Maxwell-Garnett model and the Fresnel equations, and the device is fabricated with a cosputtering deposition system.     

An experimental correlation study between field–target overlap and sensitivity of surface plasmon resonance biosensors based on sandwiched immunoassays

In this report, we have studied the effectiveness of field–target overlap to evaluate detection sensitivity of surface plasmon resonance (SPR) biosensors. The investigation used theoretical analysis based on the transfer matrix method, which was experimentally confirmed by thin film-based detection in sandwich and reverse sandwich immunoglobulin G (IgG) assays. Both theoretical and experimental results show that strong correlation exists between the overlap and the sensitivity with the coefficient of correlation higher than 95% in all the cases that we have considered. We have also confirmed the correlation in diffraction grating-based SPR measurement of IgG/anti-IgG interactions. The correlation elucidates the mechanism behind the far-field detection sensitivity of SPR biosensors and can lead to the enhancement of SPR biosensing with molecular scale sensitivity.     

Improvement of plasmonic field-matter interaction by subwavelength dielectric gratings

We experimentally and theoretically investigate that detection sensitivity in surface plasmon resonance (SPR) biosensors can be significantly enhanced by employing subwavelength dielectric gratings deposited on a gold film. The enhancement originates from an improvement of field-matter interaction: enhanced evanescent field intensity at the binding region and increased surface reaction area. Using a large-area SiO₂ grating array fabricated by nanoimprint lithography, experimental sensor performance measured by parylene film coating shows that the SPR substrates combined with a dielectric grating provide a notable sensitivity improvement compared to a conventional bare gold film. We also demonstrate that plasmon field can be more confined and enhanced at the dielectric gratings with a larger width. The proposed SPR structure could potentially be useful in a variety of plasmonic applications including high-sensitivity biosensors.     

Surface plasmon resonance characterization of thermally evaporated thin gold films

The heterogeneous character of thin gold films prepared by thermal evaporation and the dependence of this heterogeneity on the rate of their deposition must be considered when exploiting their optical properties for biosensor purposes. For instance, the performance of thin gold films for surface plasmon resonance (SPR) biosensors may drastically be degraded if care is not taken to prepare a film with a high fraction of gold (>95%). We use three different models to interpret the SPR response of gold films prepared by thermal evaporation. We show that the interpretation of the SPR curves requires considering both a global heterogeneity of the gold films and a surface roughness. Our conclusions are further corroborated by scanning surface plasmon microscope (SSPM) images of these thin gold films.     

Toward single-molecule detection with sensors based on propagating surface plasmons

Surface plasmon resonance (SPR) sensors are known to be able to detect very low surface concentrations of (bio)molecules on macroscopic areas. To explore the potential of SPR biosensors to achieve single-molecule detection, we have minimized the read-out area (to ～64 μm²) by employing a sensor system based on spectroscopy of surface plasmons generated on a diffractive structure via a microscope objective and light collection through a small aperture. This approach allows for decreasing the number of detected molecules by 3 orders of magnitude compared to state-of-the-art SPR sensors. A protein monolayer has been shown to produce a response of 5000 times the baseline noise, suggesting that as few as ～500 proteins could be detected by the sensor.     

Surface plasmon resonance (SPR) reflectance imaging: Far-field recognition of near-field phenomena

The surface plasmon resonance (SPR) reflectance imaging technique provides a label-free visualization tool to characterize the near-field fluidic transport properties within 100 nm from the solid surface. The key idea is that the SPR reflectance intensity varies with the near-field refractive index (RI) of the test fluid, which in turn depends on the micro- and nano-fluidic scalar properties such as concentrations, temperatures, and phase changes, occurring in the near-field. As essential knowledge to understand and implement the SPR reflectance imaging technique, this paper presents discussions on the basics of surface plasmon polaritons (SPPs), surface plasmon resonance (SPR), setup of the SPR reflectance imaging system, and the SPR reflectance imaging resolution. The second part of the paper elaborates the applications of the SPR imaging sensor technique in characterizing the near-field fingerprints of nanofluidic evaporative self-assembly.     

Design of Highly Sensitive Surface Plasmon Resonance Sensors Using Planar Metallic Films Closely Coupled to Nanogratings

We investigate the sensitivity enhancement of surface plasmon resonance （SPR） sensors using planar metallic films closely coupled to nanogratings. The strong coupling between localized surface plasmon resonances （LSPRs） presenting in metallic nanostructures and surface plasmon polaritons （SPPs） propagating at the metallic film surface leads to changes of resonance reflection properties, resulting in enhanced sensitivity of SPR sensors. The effects of thickness of the metallic films, grating period and metal materials on the refractive index sensitivity of the device are investigated. The refractive index sensitivity of nanograting-based SPR sensors is predicted to be about 543 nm/RIU （refractive index unit） using optimized structure parameters. Our study on SPR sensors using planar metallic films closely coupled to nanogratings demonstrates the potential for significant improvement in refractive index sensitivity.