DNA‐Mediated Self‐Assembly of Plasmonic Antennas with a Single Quantum Dot in the Hot Spot

DNA self‐assembly is a powerful tool to arrange optically active components with high accuracy in a large parallel manner. A facile approach to assemble plasmonic antennas consisting of two metallic nanoparticles (40 nm) with a single colloidal quantum dot positioned at the hot spot is presented here. The design approach is based on DNA complementarity, stoichiometry, and steric hindrance principles. Since no intermediate molecules other than short DNA strands are required, the structures possess a very small gap (≈ 5 nm) which is desired to achieve high Purcell factors and plasmonic enhancement. As a proof‐of‐concept, the fluorescence emission from antennas assembled with both conventional and ultrasmooth spherical gold particles is measured. An increase in fluorescence is obtained, up to ≈30‐fold, compared to quantum dots without antenna.     

Fluorescence Enhancement on Large Area Self‐Assembled Plasmonic‐3D Photonic Crystals

Discontinuous plasmonic‐3D photonic crystal hybrid structures are fabricated in order to evaluate the coupling effect of surface plasmon resonance and the photonic stop band. The nanostructures are prepared by silver sputtering deposition on top of hydrophobic 3D photonic crystals. The localized surface plasmon resonance of the nanostructure has a symbiotic relationship with the 3D photonic stop band, leading to highly tunable characteristics. Fluorescence enhancements of conjugated polymer and quantum dot based on these hybrid structures are studied. The maximum fluorescence enhancement for the conjugated polymer of poly(5‐methoxy‐2‐(3‐sulfopropoxy)‐1,4‐phenylenevinylene) potassium salt by a factor of 87 is achieved as compared with that on a glass substrate due to the enhanced near‐field from the discontinuous plasmonic structures, strong scattering effects from rough metal surface with photonic stop band, and accelerated decay rates from metal‐coupled excited state of the fluorophore. It is demonstrated that the enhancement induced by the hybrid structures has a larger effective distance (optimum thickness ≈130 nm) than conventional plasmonic systems. It is expected that this approach has tremendous potential in the field of sensors, fluorescence‐imaging, and optoelectronic applications.     

A Self-Assembled Plasmonic Substrate for Enhanced Fluorescence Resonance Energy Transfer

Fluorescence resonance energy transfer (FRET) has found widespread uses in biosensing, molecular imaging, and light harvesting. Plasmonic metal nanostructures offer the possibility of engineering photonic environment of specific fluorophores to enhance the FRET efficiency. However, the potential of plasmonic nanostructures to enable tailored FRET enhancement on planar substrates remains largely unrealized, which are of considerable interest for high-performance on-surface bioassays and photovoltaics. The main challenge lies in the necessitated concurrent control over the spectral properties of plasmonic substrates to match that of fluorophores and the fluorophore–substrate spacing. Here, a self-assembled plasmonic substrate based on polydopamine (PDA)-coated plasmonic nanocrystals is developed to effectively address this challenge. The PDA coating not only drives interfacial self-assembly of the nanocrystals to form closely packed arrays with customized optical properties, but also can serve as a tailored nanoscale spacer between the fluorophores and plasmonic nanocrystals, which collectively lead to optimized fluorescence enhancement. The biocompatible plasmonic substrate that allows convenient bioconjugation imparted by PDA has afforded improved FRET efficiency in DNA microarray assay and FRET imaging of live cells. It is envisioned that the self-assembled plasmonic substrates can be readily integrated into fluorescence-based platforms for diverse biomedical and photoconversion applications.     

Wide‐Range Tunable Fluorescence Lifetime and Ultrabright Luminescence of Eu‐Grafted Plasmonic Core–Shell Nanoparticles for Multiplexing

Wide‐range, well‐separated, and tunable lifetime nanocomposites with ultrabright fluorescence are highly desirable for applications in optical multiplexing such as multiplexed biological detection, data storage, and security printing. Here, a synthesis of tunable fluorescence lifetime nanocomposites is reported featuring europium chelate grafted onto the surface of plasmonic core–shell nanoparticles, and systematically investigated their optical performance. In a single red color emission channel, more than 12 distinct fluorescence lifetime populations with high fluorescence efficiency (up to 73%) are reported. The fluorescence lifetime of Eu‐grafted core–shell nanoparticles exhibits a wider tunable range, possesses larger lifetime interval and is more sensitive to separation distance than that of ordinary Eu‐doping core–shell type. These superior performances are attributed to the unique nanostructure of Eu‐grafed type. In addition, these as‐prepared nanocomposites are used for security printing to demonstrate optical multiplexing applications. The optical multiplexing experiments show an interesting pseudo‐information “a rabbit in a well” and conceal the real message “NKU.”     

Synergistic Modulation of Surface Interaction to Assemble Metal Nanoparticles into Two‐Dimensional Arrays with Tunable Plasmonic Properties

A simple strategy based on the synergistic modulation of inter‐particle and substrate‐particle interaction is applied for the large‐scale fabrication of two‐dimensional (2D) Au and Ag nanoparticle arrays. The surface charge of the substrate is used to redistribute the double layer electric charges on the particles and to modulate the inter‐particle distance within the 2D nanoparticle arrays on the substrate. The resultant arrays, with a wide range of inter‐particle distances, display tunable plasmonic properties. It can be foreseen that such 2D nanoparticle arrays possess potential applications as multiplexed colorimetric sensors, integrated devices and antennas. Herein, it is demonstrated that these arrays can be employed as wavelength‐selective substrates for multiplexed acquisition of surface‐enhanced Raman scattering (SERS) spectra. This simple one step process provides an attractive and low cost strategy to produce high quality and large area 2D ordered arrays with tunable properties.     

Interfacial Capillary‐Force‐Driven Self‐Assembly of Monolayer Colloidal Crystals for Supersensitive Plasmonic Sensors

Colloidal lithography technology based on monolayer colloidal crystals (MCCs) is considered as an outstanding candidate for fabricating large‐area patterned functional nanostructures and devices. Although many efforts have been devoted to achieve various novel applicatons, the quality of MCCs, a key factor for the controllability and reproducibility of the patterned nanostructures, is often overlooked. In this work, an interfacial capillary‐force‐driven self‐assembly strategy (ICFDS) is designed to realize a high‐quality and highly‐ordered hexagonal monolayer MCCs array by resorting the capillary effect of the interfacial water film at substrate surface as well as controlling the zeta potential of the polystyrene particles. Compared with the conventional self‐assembly method, this approach can realize the reself‐assembly process on the substrate surface with few colloidal aggregates, vacancy, and crystal boundary defects. Furthermore, various typical large‐scale nanostructure arrays are achieved by combining reactive ion etching, metal‐assisted chemical etching, and so forth. Specifically, benefiting from the as‐fabricated high‐quality 2D hexagonal colloidal crystals, the surface plasmon resonance (SPR) sensors achieve an excellent refractive index sensitivity value of 3497 nm RIU^?1, which is competent for detecting bovine serum albumin with an ultralow concentration of 10^?8 m . This work opens a window to prepare high‐quality MCCs for more potential applications.     

Photonic Microcapsules Containing Single‐Crystal Colloidal Arrays with Optical Anisotropy

Colloidal particles with a repulsive interparticle potential spontaneously form crystalline lattices, which are used as a motif for photonic materials. It is difficult to predict the crystal arrangement in spherical volume as lattices are incompatible with a spherical surface. Here, the optimum arrangement of charged colloids is experimentally investigated by encapsulating them in double‐emulsion drops. Under conditions of strong interparticle repulsion, the colloidal crystal rapidly grows from the surface toward the center of the microcapsule, forming an onion‐like arrangement. By contrast, for weak repulsion, crystallites slowly grow and fuse through rearrangement to form a single‐crystal phase. Single‐crystal structure is energetically favorable even for strong repulsion. Nevertheless, a high energy barrier to colloidal rearrangement kinetically arrests the onion‐like structure formed by heterogeneous nucleation. Unlike the isotropic onion‐shaped product, the anisotropic single‐crystal‐containing microcapsules selectively display—at certain orientations but not others—one of the distinct colors from the various crystal planes.     

Silk Fluorescence Collimator for Ultrasensitive Humidity Sensing and Light‐Harvesting in Semitransparent Dye‐Sensitized Solar Cells

This work examines the self‐collimation effect of silk materials on fluorescence emission/detection. A macroscopic regulation strategy, coupled with meso‐reconstruction and meso‐functionalization, is adopted to amplify the fluorescence emission of organic fluorescent dyes (i.e., Rhodamine 6G (R6G)) using silk photonic crystal (PC) films. The fluorescence emission can be linearly enhanced or inhibited by a PC as a result of the photonic bandgap coupling with the excitation light and/or emission light. Depending on the design of the silk fluorescence collimator, the emission can reach 49.37 times higher than the control. The silk fluorescence collimator can be applied to achieve significant benefits: for instance, as a humidity sensor, it provides good reproducibility and a sensitivity of 28.50 a.u./% relative humidity, which is 80.78 times higher than the sensitivity of the control, and as a novel curtain, it raises the energy conversion efficiency of the semitransparent dye‐sensitized solar cells (DSSCs) by 16%.     

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self‐assembly strategy through a one‐step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size‐ and distance‐dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near‐field plasmonic properties.