We demonstrate selective trapping or rotation of optically isotropic dielectric microparticles by plasmonic near field in a single gold plasmonic Archimedes spiral. Depending on the handedness of ...circularly polarized excitation, plasmonic near fields can be selectively engineered into either a focusing spot for particle trapping or a plasmonic vortex for particle rotation. Our design provides a simple solution for subwavelength optical manipulation and may find applications in micromechanical and microfluidic systems.
Au–Pd core–shell nanocrystals with tetrahexahedral (THH), cubic, and octahedral shapes and comparable sizes were synthesized. Similar‐sized Au and Pd cubes and octahedra were also prepared. These ...nanocrystals were used for the hydrogen‐evolution reaction (HER) from ammonia borane. Light irradiation can enhance the reaction rate for all the catalysts. In particular, Au–Pd THH exposing {730} facets showed the highest turnover frequency for hydrogen evolution under light with 3‐fold rate enhancement benefiting from lattice strain, modified surface electronic state, and a broader range of light absorption. Finite‐difference time‐domain (FDTD) simulations show a stronger electric field enhancement on Au–Pd core–shell THH than those on other Pd‐containing nanocrystals. Light‐assisted nitro reduction by ammonia borane on Au–Pd THH was also demonstrated. Au–Pd tetrahexahedra supported on activated carbon can act as a superior recyclable plasmonic photocatalyst for hydrogen evolution.
Facets of HER personality: Au–Pd core–shell tetrahexahedral nanocrystals exposing the {730} facet act as efficient plasmonic photocatalyst with the highest turnover frequency value for the hydrogen‐evolution reaction (HER) from ammonia borane under light irradiation.
It has long been surmised that the circular polarization of luminescence (CPL) emitted by a chiral molecule or a molecular assembly should vary with the direction in which the photon is emitted. ...Despite its potential utility, this anisotropic CPL has not yet been demonstrated at the level of single molecules or supramolecular assemblies. Here we show that conjugated polymers bearing chiral side chains self-assemble into solid microspheres with a twisted bipolar interior, which are formed via liquid–liquid phase separation and subsequent condensation into a cholesteric lyotropic liquid crystalline mesophase. The resultant microspheres, when dispersed in methanol, exhibit CPL with a g lum value as high as 0.23. The microspheres are mechanically robust enough to be handled with a microneedle under ambient conditions, allowing comprehensive examination of the angular anisotropy of CPL. The single microsphere is found to exhibit distinct angularly anisotropic birefringence and CPL with g lum up to ∼0.5 in the equatorial plane, which is 2.5-fold greater than that along the polar axis. Such optically anisotropic solid materials are important for the application to next-generation microlight-emitting and visualizing devices as well as for fundamental optics studies of chiral light–matter interaction.
Conspectus For optical and electronic applications of supramolecular assemblies, control of the hierarchical structure from nano- to micro- and millimeter scale is crucial. Supramolecular chemistry ...controls intermolecular interactions to build up molecular components with sizes ranging from several to several hundreds of nanometers using bottom-up self-assembly process. However, extending the supramolecular approach up to a scale of several tens of micrometers to construct objects with precisely controlled size, morphology, and orientation is challenging. Especially for microphotonics applications such as optical resonators and lasers, integrated optical devices, and sensors, a precise design of a micrometer-scale object is required. In this Account, we review the recent progress on precise control of microstructures from π-conjugated organic molecules and polymers, which work as micro-photoemitters and are suitable for optical applications. After the introduction on the importance of the control of the hierarchical structures from molecular assembly, we review supramolecular methodology for assembling molecules and supramolecules to form microstructures such as spheres and polygons with precisely controlled morphology and molecular orientations. The resultant microstructures act as anisotropic emitters of circularly polarized luminescence. We report that synchronous crystallization of π-conjugated chiral cyclophanes forms concave hexagonal pyramidal microcrystals with homogeneous size, morphology, and orientation, which clearly paves the way for the precise control of skeletal crystallization under kinetic control. Furthermore, we show microcavity functions of the self-assembled micro-objects. The self-assembled π-conjugated polymer microspheres work as whispering gallery mode (WGM) optical resonators, where the photoluminescence exhibits sharp and periodic emission lines. The spherical resonators with molecular functions act as long-distance photon energy transporters, convertors, and full-color microlasers. Fabrication of microarrays with photoswitchable WGM microresonators by the surface self-assembly technique realizes optical memory with physically unclonable functions of WGM fingerprints. All-optical logic operations are demonstrated by arranging the WGM microresonators on synthetic and natural optical fibers, where the photoswitchable WGM microresonators act as a gate for light propagation via a cavity-mediated energy transfer cascade. Meanwhile, the sharp WGM emission line is appropriate for utilization as optical sensors for monitoring the mode shift and mode splitting. The resonant peaks sensitively respond to humidity change, absorption of volatile organic compounds, microairflow, and polymer decomposition by utilizing structurally flexible polymers, microporous polymers, nonvolatile liquid droplets, and natural biopolymers as media of the resonators. We further construct microcrystals from π-conjugated molecules with rods and rhombic plates, which act as WGM laser resonators with light-harvesting function. Our developments, precise design and control of organic/polymeric microstructures, form a bridge between nanometer-scale supramolecular chemistry and bulk materials and pave the way toward flexible micro-optics applications.
Metasurfaces comprising 3D chiral structures have shown great potential in chiroptical applications such as chiral optical components and sensing. So far, the main challenges lie in the ...nanofabrication and the limited operational bandwidth. Homogeneous and localized broadband near‐field optical chirality enhancement has not been achieved. Here, an effective nanofabrication method to create a 3D chiral metasurface with far‐ and near‐field broadband chiroptical properties is demonstrated. A focused ion beam is used to cut and stretch nanowires into 3D Archimedean spirals from stacked films. The 3D Archimedean spiral is a self‐similar chiral fractal structure sensitive to the chirality of light. The spiral exhibits far‐ and near‐field broadband chiroptical responses from 2 to 8 µm. With circularly polarized light (CPL), the spiral shows superior far‐field transmission dissymmetry and handedness‐dependent near‐field localization. With linearly polarized excitation, homogeneous and highly enhanced broadband near‐field optical chirality is generated at a stably localized position inside the spiral. The effective yet straightforward fabrication strategy allows easy fabrication of 3D chiral structures with superior broadband far‐field chiroptical response as well as strongly enhanced and stably localized broadband near‐field optical chirality. The reported method and chiral metasurface may find applications in broadband chiral optics and chiral sensing.
An effective and single‐step nanofabrication method for a broadband 3D chiral metasurface is demonstrated in this work. The metasurface consists of 3D self‐similar Archimedean spirals and shows very broadband and significant chiroptical properties in the infrared regime. This work paves a novel route toward ultracompact chiral optical components and chiroptical sensing.
Plasmonic nanoantennas mediate far and near optical fields and confine the light to subwavelength dimensions. The spatial organization of nanoantenna elements is critical as it affects the ...interelement coupling and determines the resultant antenna mode. To couple quantum emitters to optical antennas, high precision on the order of a few nm with respect to the antenna is necessary. As an emerging nanofabrication technique, DNA origami has proven itself to be a robust nanobreadboard to obtain sub‐5 nm positioning precision for a diverse range of materials. Eliminating the need for expensive state‐of‐the‐art top‐down fabrication facilities, DNA origami enables cost‐efficient implementation of nanoscale architectures, including novel nanoantennas. The ability of DNA origami to deterministically position single quantum emitters into nanoscale hotspots further boosts the efficiency of light–matter interaction controlled via optical antennas. This review recapitulates the recent progress in plasmonic nanoantennas assisted by DNA origami and focuses on their various configurations. How those nanoantennas act on the emission and absorption properties of quantum emitters positioned in the hotspots is explicitly discussed. In the end, open challenges are outlined and future possibilities lying ahead are pointed out for this powerful triad of biotechnology, nanooptics, and photophysics.
DNA origami technology enables designable spatial arrangement of nanomaterials. This capability allows deterministically positioning single quantum emitters at the hotspots of plasmonic nanoantennas. When quantum emitters couple efficiently to plasmonic nanoantennas, their emission properties can be substantially modified, rendering DNA origami‐assisted plasmonic nanoantennas a promising platform for manipulating the emission of quantum emitters.
An experimentally realizable prototype optical nanocircuit consisting of a receiving and an emitting nanoantenna connected by a two-wire optical transmission line is studied using finite-difference ...time- and frequency-domain simulations. To optimize the coupling between optical nanocircuit elements we apply impedance matching concepts in analogy to radio frequency technology. We show that the degree of impedance matching, and in particular the impedance of the emitting nanoantenna, can be inferred from the experimentally accessible standing wave pattern on the transmission line. We demonstrate the possibility of matching the nanoantenna impedance to the transmission line by variations of the antenna length and width realizable by modern microfabrication techniques. The radiation efficiency of the emitting antenna also depends on its geometry but is independent of the degree of impedance matching. The case study presented here provides the basis for experimental realizations of general optical nanocircuits based on readily available gold nanostructures and a large variety of derived novel devices.
We present a new design of plasmonic nanoantenna with slant gap for optical chirality engineering. At resonance, the slant gap provides highly enhanced electric field parallel to external magnetic ...field with a phase delay of π/2, resulting in enhanced optical chirality. We show by numerical simulations that upon linearly polarized excitation our nanoantenna can generate near field with enhanced optical chirality which can be tuned by the slant angle and resonance condition. Our design allows chiral analysis with linearly polarized light and may find applications in circular dichroism analysis of chiral matter at surface.
Low‐threshold organic microlasers are demanded for advanced optical applications such as nano/micrometer scale memory, sensing, and communication tools, and further valuable for future electrically ...driven laser applications. In this paper, it is demonstrated that various highly fluorescent conjugated polymers self‐assemble to form single‐component microspheres that exhibit, upon femtosecond pumping to a single microsphere, whispering gallery mode (WGM) lasing with blue, green, and red emission colors. In particular, the microsphere consisting of polyfluorene shows the lowest threshold fluence as low as 1.5 µJ cm−2 and high photostability against successive pumping of >105 pulse. The threshold fluence is further reduced by one fourth (0.37 µJ cm−2) by mounting the microspheres on an Ag‐coated substrate, where a mirror effect of the Ag layer enhances efficiency of the photoluminescence confinement with a minor effect of plasmonic near‐field. Considering the intrinsic charge injection and transport properties, π‐conjugated polymer microsphere resonators will be possible materials for electrically pumped WGM luminescence.
Self‐assembled, single‐component conjugated polymer microspheres exhibit whispering gallery mode lasing upon femtosecond laser pumping with the lasing threshold as low as one micro Joule per square centimeter. The threshold fluence is further reduced by one fourth by mounting the microspheres on an Ag‐coated substrate, which is among the lowest for that ever reported with dye‐doped polymer lasers.
PDF
