Plasmon–Exciton Interactions: Spontaneous Emission and Strong Coupling

The extraordinary optical properties of surface plasmons in metal nanostructures provide the possibilities to enhance and accelerate the spontaneous emission, and manipulate the decay and emission processes of quantum emitters. The extremely small mode volume of plasmonic nanocavities also benefits the realization of plasmon–exciton strong coupling. Here, the progress on the study of plasmon modified spontaneous emission and plasmon–exciton strong coupling are reviewed. The fundamentals of surface plasmons and quantum emitters, and the methods for assembling coupling systems of plasmonic nanostructures and quantum emitters are first introduced. Then the major aspects of plasmon modified spontaneous emission, including emission intensity, lifetime, spectral profile, direction, polarization, and energy transfer are reviewed. The coupling of quantum emitters and plasmonic waveguides is then discussed. Next, the developments of strong coupling between plasmonic structures and various quantum emitters are reviewed. Finally a few applications are highlighted followed by conclusions and outlook.     

Shell-Isolated Plasmonic Nanostructures for Biosensing,Catalysis, and Advanced Nanoelectronics

Shell-isolated nanostructures, consisting of an inert shell and a plasmonic core, have recently been intensively explored for biosensing, catalysis, and nanoelectronics applications owing to their functional shells and unique plasmonic properties. Such designer shell-isolated plasmonic nanostructures possess the potential to improve the detectability of biosensors and provide powerful platforms to explore in-depth plasmon enhancement principles and finally boost significantly their photo(electro)catalytic efficiency. In addition, such structural optimization and interface nanoengineering promote solid developments of advanced nanoelectronics toward real applications, revealing new electron transport mechanisms and enabling exploration of new functional and integrated optoelectronic devices. In this overview, the state-of-the-art progresses of shell-isolated plasmonic nanostructures (SHIPNSs) in the field of biosensing, photo(electro)catalysis, and nanoelectronics is summarized, focusing on the superiority of the core–shell materials in exploration of biosensing, catalytic enhancement mechanisms, and electron transport principles. A brief overview of synthetic methods is introduced, and then the significant importance of shell-isolated nanomaterials in fabrication and promising direction for future development and challenges are discussed.     

表面等离子阵列结构中的耦合增强反射效应其红外光谱增强特性研究

使用聚焦离子束刻蚀的方法制备了不同间距的表面等离子结构阵列,研究了由方形和圆形所构成的阵列在不同间距下的光学反应.实验表明,粒子之间耦合效应随着间距的显著减小而逐渐变强,从弱耦合变化为强耦合状态.当间距小于30 nm时,发现耦合增强的反射效应,共振波长也会随着间距的减小而发生红移.将制备的超小间距纳米阵列和傅里叶变换光谱仪的ATR附件相耦合,实验验证了相关阵列结构在红外光谱增强方面的显著效果.相关的发现和表面等离子阵列结构可以在传感、探测和光谱增强等方面取得一定的应用.     

Gold Nanobipyramid‐Supported Silver Nanostructures with Narrow Plasmon Linewidths and Improved Chemical Stability

Silver nanostructures with narrow plasmon linewidths and good chemical stability are strongly desired for plasmonic applications. Herein, a facile method is discussed for the preparation of Ag nanostructures with narrow plasmon linewidths and improved chemical stability through Ag overgrowth on monodispersed Au nanobipyramids. Structural evolution from bipyramid through rice to rod is observed, indicating that Ag atoms are preferentially deposited on the side surfaces of Au nanobipyramids. The resultant (Au nanobipyramid)@Ag nanostructures possess high size and shape uniformities, and much narrower plasmon linewidths than other Ag nanostructures. The spectral evolution of the supported Ag nanostructures is ascertained by both ensemble and single‐particle characterizations, together with electrodynamic simulations. Systematic measurements of the refractive index sensing characteristics indicate that Ag nanostructures in this study possess high index sensitivities and figure of merit (sensitivity divided by linewidth) values. Moreover, Ag nanostructures in this study exhibit greatly improved chemical stability. The superior sensing capability of Ag nanostructures in this study is further demonstrated by the detection of sulfide ions at a relatively low detection limit. Taken together, results of this study show that the Au‐nano­bipyramid‐supported Ag nanostructures will be an outstanding candidate for the design of ultrasensitive plasmonic sensing devices as well as for the development of other plasmon‐enabled technological applications.     

Selective Pd Deposition on Au Nanobipyramids and Pd Site‐Dependent Plasmonic Photocatalytic Activity

The synthesis of anisotropic metal nanostructures is strongly desired for exploring plasmon‐enabled applications. Herein, the preparation of anisotropic Au/SiO₂ and Au/SiO₂/Pd nanostructures is realized through selective silica coating on Au nanobipyramids. For silica coating at the ends of Au nanobipyramids, the amount of coated silica and the overall shape of the coated nanostructures exhibit a bell‐shaped dependence on the cationic surfactant concentration. For both end and side silica coating on Au nanobipyramids, the size of the silica component can be varied by changing the silica precursor amount. Silica can also be selectively deposited on the corners or facets of Au nanocubes, suggesting the generality of this method. The blockage of the predeposited silica component on Au nanobipyramids enables further selective Pd deposition. Suzuki coupling reactions carried out with the different bimetallic nanostructures functioning as plasmonic photocatalysts indicate that the plasmonic photocatalytic activity is dependent on the site of Pd nanoparticles on Au nanobipyramids. Taken together, these results suggest that plasmonic hot spots play an important role in hot‐electron‐driven plasmonic photocatalysis. This study opens up a promising route to the construction of anisotropic bimetallic nanostructures as well as to the design of bimetallic plasmonic‐catalytic nanostructures as efficient plasmonic photocatalysts.     

Growth and Device Application of CdSe Nanostructures

Inorganic semiconductor nanostructures have attracted increasing interest in recent years because of their distinguishable role in fundamental studies and technical applications, mainly due to their size‐ and shape‐dependent properties and flexible processing methods. The use of such nanostructures in optic, optoelectric, and piezoelectric prospects is expected to play a crucial role in future nanoscale devices. Cadmium selenide (CdSe), a well‐known direct bandgap II‐VI semiconductor in which the bandgap favors absorption over a wide range of the visible spectrum, has been a promising material for applications in such fields as photodetectors, field‐effect transistors (FETs), field emitters, solar cells, light‐emitting diodes (LEDs), memory devices, biosensors, and biomedical imaging. The research on CdSe nanostructures has made remarkable progress in the last few years. The research activities on CdSe nanostructures including various methods for the synthesis of CdSe nanostructures and the unique properties and device applications of these nanostructures are reviewed. Potential future directions of this research area are also highlighted.     

Plasmonic Nanoneedle Arrays with Enhanced Hot Electron Photodetection for Near-IR Imaging

Hot electron photodetection based on metallic nanostructures is attracting significant attention due to its potential to overcome the limitation of the traditional semiconductor bandgap. To enable efficient hot electron photodetection for practical applications, it is necessary to achieve broadband and perfect light absorption within extremely thin plasmonic nanostructures using cost-effective fabrication techniques. In this study, an ultrahigh optical absorption (up to 97.3% in average across the spectral range of 1200−2400 nm) is demonstrated in the ultrathin plasmonic nanoneedle arrays (NNs) with thickness of 10 nm, based on an all-wet metal-assisted chemical etching process. The efficient hot electron generation, transport, and injection at the nanoscale apex of the nanoneedles facilitate the photodetector to achieve a record low noise equivalent power (NEP) of 4.4 × 10⁻¹² W Hz^−0.5 at the wavelength of 1300 nm. The hot-electron generation and injection process are elucidated through a transport model based on a Monte Carlo approach, which quantitatively matches the experimental data. The photodetector is further integrated into a light imaging system, as a demonstration of the exceptional imaging capabilities at the near-IR regime. The study presents a lithography-free, scalable, and cost-effective approach to enhance hot electron photodetection, with promising prospects for future imaging systems.     

叠层圆柱台表面等离激元器件的共振特性

基于金属纳米结构增强光与物质的相互作用,调控光学响应是光学前沿研究。金属纳米结构能显著增强电磁场和热点空间位置调控,是表面等离激元器件应用的关键。借鉴衍射光学元件设计思想,文中提出一种简单的多尺度叠层圆柱台（double stacked nanocone,DSC）金属纳米结构,实现近/远场深度调控。在给定激发条件下,DSC纳米结构中腔模与局域表面等离激元模式间产生杂化,实现多尺度级联场增强,远场响应也得到有效调制,且热点能有效地定位到纳米结构的上表面。进一步,提出并研究了掩模重构的纳米加工方法,低成本、可控地制备了DSC纳米结构,工艺控制是三台阶DSC器件特性的关键,实验结果与理论设计一致。     

Photocontrollable Chiral Switching and Selection in Self‐Assembled Plasmonic Nanostructure

Reversible photocontrol of dynamic chirality in self‐assembly systems is of great importance in exploitations of artificial nanomachines for scientific and industrious applications. Here, a new strategy is proposed for achieving optically chiral controls based on photoswitchable plasmonic nanostructures. Chiral plasmonic nanoassemblies that are responsive to optomechanical perturbations exerted by circular polarized light (CPL) in the visible (vis)/near infrared (NIR) region are designed. The reversible photoswitching between opposite chiral states is verified by circular dichroism (CD) spectral signals. Theoretical simulations reveal the key role of optical torques in driving this chiral switching. By regulating light polarization or tuning light frequency to excite different plasmonic modes of the nanostructures, such an optomechanically driven chiral switching can enable a directed mirror‐symmetry breaking and selective chiral amplification in nanoassemblies. This plasmon‐based photoswitching nanosystem can operate at the optical transparent window, showing particular advantages over most of the molecular photoswitches for applications in living systems.     

基于等离激元纳米结构非对称集成的二维材料自驱动光响应增强的研究进展（特邀）

金属-二维材料-金属是最常见的二维材料光探测器件的结构。由于结构简单、易于集成,该类器件受到最广泛的关注和研究。其自驱动光探测的模式具有很低的暗电流,有望成为高性能红外探测的新途径。然而金属-二维材料-金属的自驱动光探测存在两个瓶颈问题:（1）反对称的金属-二维材料结区引起的泛光照射下光响应的抵消;（2）二维材料有限光吸收导致的低响应率。文中介绍了利用等离激元纳米结构的非对称集成引入非对称的光耦合,从而打破泛光照射下二维材料与两端电极接触区域产生的光电流的对称性,实现净的自驱动光响应;同时利用等离激元纳米结构产生的局域强光场提高二维材料光吸收率和光响应率的一系列研究进展。在石墨烯等离激元纳米谐振腔复合结构中,实现两个电极附近的光响应对比度超过100倍,突破了对称光耦合导致的光响应抵消的难题。由于具有将入射光耦合成局域模式的优越能力,等离激元纳米谐振腔比亚波长金属光栅更有效地提高石墨烯响应率一个数量级以上。     

Tailored Plasmonic Gratings for Enhanced Fluorescence Detection and Microscopic Imaging

The ability to precisely control the pattern of metallic structures at the micro‐ and nanoscale for surface plasmon coupling has been demonstrated to be essential for signal enhancement in fields such as fluorescence and surface‐enhanced Raman scattering. In the present study, a series of silver coated gratings with tailored duty ratio and depth and a periodical pitch of 400 nm are designed and implemented. The influence of the grating profile on plasmonic properties and the corresponding enhancement factor are investigated by angular scanning measurement of reflectivity and fluorescence intensity and by finite difference time domain simulation. The application of the substrate in the enhanced fluorescence imaging detection of labeled protein is also investigated. This substrate has a wide range of potential applications in areas including biodiagnostics, imaging, sensing, and photovoltaic cells.     

Ultrasensitive Plasmonic Response of Bimetallic Au/Pd Nanostructures to Hydrogen

Hydrogen detection is crucial for the safety of all hydrogen‐related applications. Compared to electrical hydrogen sensors, which usually suffer from possible electric sparks, optical hydrogen sensors offer advantages of remote and contact‐free readout and therefore the avoidance of spark generation. Herein, bimetallic Au/Pd nanostructure monolayers that exhibit ultrasensitive plasmonic response to hydrogen are reported. Bimetallic Au/Pd nanostructures with continuous and discontinuous Pd shells are prepared. The plasmonic response to hydrogen is monitored by measuring the extinction spectra of the ensemble Au/Pd nanostructures deposited on glass slides. Introduction of hydrogen induces red plasmon shifts, which become larger for the nanostructures with thicker Pd shells. For the nanostructures with continuous Pd shell, the plasmon shift can reach 56 nm at the hydrogen volume concentration below the explosion limit. The plasmon resonance wavelength displays an excellent linear dependence on the hydrogen volume concentration below 1%. The detection limit in the experiments reaches 0.2%. The nanostructures with discontinuous Pd shell show smaller plasmon shifts than those with continuous Pd shell. The extinction measurements on the ensemble nanostructures supported on transparent substrates and the unprecedentedly large plasmon shifts and sensitivity make the results very promising for the development of practical optical hydrogen sensors.     

Hybrid Metasurfaces of Plasmonic Lattices and 2D Materials

Plasmonic metasurfaces can significantly enhance the interaction between light and 2D materials. Hybrid structures of plasmonic lattices and 2D materials show great promise for both fundamental and practical studies because of their unprecedented ability for precise manipulation of light at the nanoscale. This review starts with an overview of the basic concepts of plasmonic lattices and optical properties of 2D materials, as well as fabrication strategies for hybrid metasurfaces. Then, the enhanced photoluminescence, quantum emission, optoelectronic detection, nonlinear process, and valleytronics in hybrid metasurfaces are summarized, and their development for nanophotonic functional devices are reviewed. Further, several compelling topics are also outlined that provide outlooks for future directions of hybrid metasurfaces such as novel structural design and high-quality fabrication, all-dielectric metasurfaces, dynamic metasurfaces, and plasmonic mediation of chemical reactions and physical processes. It is believed that hybrid metasurfaces of plasmonic lattices and 2D materials can open prospects for versatile platforms for light-matter interactions and contribute to the revolutions on nanophotonic devices.     

Self‐Assembly of Nanoparticle‐Spiked Pillar Arrays for Plasmonic Biosensing

Plasmonic biosensors have demonstrated superior performance in detecting various biomolecules with high sensitivity through simple assays. Scaled‐up, reproducible chip production with a high density of hotspots in a large area has been technically challenging, limiting the commercialization and clinical translation of these biosensors. A new fabrication method for 3D plasmonic nanostructures with a high density, large volume of hotspots and therefore inherently improved detection capabilities is developed. Specifically, Au nanoparticle‐spiked Au nanopillar arrays are prepared by utilizing enhanced surface diffusion of adsorbed Au atoms on a slippery Au nanopillar arrays through a simple vacuum process. This process enables the direct formation of a high density of spherical Au nanoparticles on the 1 nm‐thick dielectric coated Au nanopillar arrays without high‐temperature annealing, which results in multiple plasmonic coupling, and thereby large effective volume of hotspots in 3D spaces. The plasmonic nanostructures show signal enhancements over 8.3 × 10⁸‐fold for surface‐enhanced Raman spectroscopy and over 2.7 × 10²‐fold for plasmon‐enhanced fluorescence. The 3D plasmonic chip is used to detect avian influenza‐associated antibodies at 100 times higher sensitivity compared with unstructured Au substrates for plasmon‐enhanced fluorescence detection. Such a simple and scalable fabrication of highly sensitive 3D plasmonic nanostructures provides new opportunities to broaden plasmon‐enhanced sensing applications.     

Etching‐Free Epitaxial Growth of Gold on Silver Nanostructures for High Chemical Stability and Plasmonic Activity

A robust method for epitaxial deposition of Au onto the surface of Ag nanostructures is demonstrated, which allows effective conversion of Ag nano­structures of various morphologies into Ag@Au counterparts, with the anisotropic ones showing excellent plasmonic properties comparable to the original Ag nanostructures while significantly enhanced stability. Sulfite plays a determining role in the success of this epitaxial deposition as it strongly complexes with gold cations to completely prevent galvanic replacement while it also remains benign to the Ag surface to avoid any ligand‐assisted oxidative etching. By using Ag nanoplates as an example, it is shown that the corresponding Ag@Au nanoplates possess remarkable plasmonic properties that are virtually Ag‐like, in clear contrast to Ag@Au nanospheres that exhibit much lower plasmonic activities than their Ag counterparts. As a result, they display high durability and activities in surface‐enhanced Raman scattering applications. This strategy may represent a general platform for depositing a noble metal on less stable metal nanostructures, thus opening up new opportunities in rational design of functional metal nanomaterials for a broad range of applications.     

多元等离子体共振纳米结构的飞秒激光加工与拉曼检测应用

以多元金属纳米薄膜(金、银)为基底,利用飞秒激光加工技术制备得到多元等离子体纳米结构,并研究了其局域表面等离子体共振效应(Local Surface Plasmon Resonance,LSPR)和表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)性能。利用时域有限差分(Finite Difference Time Domain,FDTD)软件模拟了不同情况下(单层金膜、金银双层金属薄膜的平面以及阵列结构)的电场分布情况。根据仿真结果,相较于平面金属膜来说,飞秒激光制备的微纳结构阵列附近区域产生电磁场增强,集中在结构边缘处,且其强度变化与预期结果基本保持一致。此外,使用浓度为10-4 M和10-6 M的罗丹明(R6G)溶液进行SERS性能测试。测试的结果表明,单层平面金膜基本没有SERS峰值信号出现,而单层金膜上制备的等离子体纳米结构附近出现峰值信号,双层金属薄膜上制备的等离子体纳米结构展现出更高的SERS峰值信号。多元金属等离子体纳米结构展示出更强的局域表面等离子体共振效应,从而在表面增强拉曼散射、光催化、生物传感等领域具有广泛的应用。     

Soft Optomechanical Systems for Sensing,Modulation, and Actuation

Soft optomechanical systems have the ability to reversibly respond to optical and mechanical external stimuli by changing their own properties (e.g., shape, size, viscosity, stiffness, color or transmittance). These systems typically combine the optical properties of plasmonic, dielectric or carbon-based nanomaterials with the high elasticity and deformability of soft polymers, thus opening the path for the development of new mechanically tunable optical systems, sensors, and actuators for a wide range of applications. This review focuses on the recent progresses in soft optomechanical systems, which are here classified according to their applications and mechanisms of optomechanical response. The first part summarizes the soft optomechanical systems for mechanical sensing and optical modulation based on the variation of their optical response under external mechanical stimuli, thereby inducing mechanochromic or intensity modulation effects. The second part describes the soft optomechanical systems for the development of light induced mechanical actuators based on different actuation mechanisms, such as photothermal effects and phase transitions, among others. The final section provides a critical analysis of the main limitations of current soft optomechanical systems and the progress that is required for future devices.     

3D Aluminum Hybrid Plasmonic Nanostructures with Large Areas of Dense Hot Spots and Long‐Term Stability

Plasmonic materials possessing dense hot spots with high field enhancement over a large area are highly desirable for ultrasensitive biochemical sensing and efficient solar energy conversion; particularly those based on low‐cost noncoinage metals with high natural abundance are of considerable practical significance. Here, 3D aluminum hybrid nanostructures (3D‐Al‐HNSs) with high density of plasmonic hot spots across a large scale are fabricated via a highly efficient and scalable nonlithographic method, i.e., millisecond‐laser‐direct‐writing in liquid nitrogen. The nanosized alumina interlayer induces intense and dual plasmonic resonance couplings between adjacent Al nanoparticles with bimodal size distribution within each of the hybrid assemblies, leading to remarkably elevated localized electric fields (or hot spots) accessible to the analytes or reactants. The 3D‐stacked nanostructure substantially raises the hot spot density, giving rise to plasmon‐enhanced light harvesting from deep UV to the visible, strong enhancement of Raman signals, and a very low limit of detection outperforming reported Al nanostructures, and even comparable to the noble metals. Combined with the long‐term stability and good reproducibility, the 3D‐Al‐HNSs hold promise as a robust low‐cost plasmonic material for applications in plasmon‐enhanced spectroscopic sensing and light harvesting.     

DNA‐Directed Self‐Assembly of Core‐Satellite Plasmonic Nanostructures: A Highly Sensitive and Reproducible Near‐IR SERS Sensor

The excitation of surface plasmons in metallic nanostructures provides an opportunity to localize light at the nanoscale, well below the scale of the wavelength of the light. The high local electromagnetic field intensities generated in the vicinity of the nanostructures through this nanofocusing effect are exploited in surface enhanced Raman spectroscopy (SERS). At narrow interparticle gaps, so‐called hot‐spots, the nanofocusing effect is particularly pronounced. Hence, the engineering of substrates with a consistently high density of hot‐spots is a major challenge in the field of SERS. Here, a simple bottom‐up approach is described for the fabrication of highly SERS‐active gold core‐satellite nanostructures, using electrostatic and DNA‐directed self‐assembly. It is demonstrated that well‐defined core‐satellite gold nanostructures can be fabricated without the need for expensive direct‐write nanolithography tools such as electron‐beam lithography (EBL). Self‐assembly also provides excellent control over particle distances on the nanoscale. The as‐fabricated core‐satellite nanostructures exhibit SERS activities that are superior to commercial SERS substrates in signal intensity and reproducibility. This also highlights the potential of bottom‐up self‐assembly strategies for the fabrication of complex, well‐defined functional nanostructures with future applications well beyond the field of sensing.     

Plasmonic Modulation of Valleytronic Emission in Two-Dimensional Transition Metal Dichalcogenides

Monolayered transition metal dichalcogenides (TMDs) are one kind of hexagonal 2D semiconductors with a direct bandgap structure. Due to the property of natural broken inversion symmetry in the lattice, the strong spin–orbit coupling of electrons in TMDs can induce degenerate levels with antiparallel spins in K and K′ valleys, which selectively respond with external light excitations. Surface plasmon resonance with efficient electromagnetic enhancement and near-field coupling provides excellent potential opportunities to modulate valley emission of TMDs. Efforts have been devoted to investigating the interaction principles and applications of this research field. This review focuses on plasmonic modulation of valleytronic emission in TMDs with surface plasmon polaritons (SPP) and localized surface plasmons (LSP) based on different modulation principles, respectively, and discusses possible research directions for future device applications.