Molecular and Supramolecular Designs of Organic/Polymeric Micro-photoemitters for Advanced Optical and Laser Applications.

ConspectusFor 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.

Impact of Plasmonic and Dielectric Substrates on the Whispering-Gallery Modes in Self-Assembled Fluorescent Semiconductor Polymer Microspheres.

In this work, the impact of metallic and dielectric conducting substrates, gold and indium tin oxide (ITO)-coated glass, on the whispering gallery modes (WGMs) of semiconductor π-conjugated polymer microspheres is investigated. Hyperspectral mapping was performed to obtain the excitation-position-dependent emission spectra of the microspheres. Substrate-dependent quenching of WGMs sensitive to mode polarization was observed and explained. On a glass substrate, both transverse-electric (TE) and transverse-magnetic (TM) WGMs are quenched due to frustrated total internal reflection. On a gold substrate, however, only the TM WGMs are allowed in symmetry to leak into surface plasmons. An atomically flat gold substrate with subwavelength slits was used to experimentally verify the leakage of WGMs into the surface plasmon polaritons (SPPs). This work provides insight into the damping mechanisms of WGMs in microspheres on metallic and dielectric substrates.

Nanoscale Hotspot-Induced Emitters in DNA Origami-Assisted Nanoantennas.

We report the observation of hotspot-induced emitters and photoluminescence enhancement of up to 42-fold from DNA origami-assisted plasmonic dimer nanoantennas upon excess polarized laser illumination. The presence of DNA and laser polarization alignment along the dimer axis are critical for the generation of bright emitters responsible for the observed PL increase. The emission spectrum reveals characteristic Raman peaks of amorphous carbon, suggesting the formation of carbon-based emitters in the nanoantenna due to the plasmonic hotspots at the longitudinal antenna resonance.

Nonlinear Optical Signal Generation Mediated by a Plasmonic Azimuthally Chirped Grating.

Plasmonic gratings are simple and effective platforms for nonlinear signal generation since they provide a well-defined momentum for photon-plasmon coupling and local hot spots for frequency conversion. Here, a plasmonic azimuthally chirped grating (ACG), which provides spatially resolved broadband momentum for photon-plasmon coupling, was exploited to investigate the plasmonic enhancement effect in two nonlinear optical processes, namely two-photon photoluminescence (TPPL) and second harmonic generation (SHG). The spatial distributions of the nonlinear signals were determined experimentally by hyperspectral mapping with ultrashort pulsed excitation. The experimental spatial distributions of nonlinear signals agree very well with the analytical prediction based on photon-plasmon coupling with the momentum of the ACG, revealing the "antenna" function of the grating in plasmonic nonlinear signal generation. This work highlights the importance of the antenna effect of the gratings for nonlinear signal generation and provides insight into the enhancement mechanism of plasmonic gratings in addition to local hot spot engineering.

Optical responses of Fano resonators in non-spectral parametric domains.

Fano resonance observed in various classical and quantum systems features an asymmetric spectral line shape. For designing nanoresonators for monochromatic applications, it is beneficial to describe Fano resonance in non-spectral parametric domains of critical structural parameters. We develop an analytical model of the parametric Fano profile based on a coupled harmonic oscillator model and theoretically demonstrate its application in describing the optical response of a series of waveguided plasmonic crystals of varying periodicity. The developed parametric Fano model may find applications in the design of monochromatic and spectrometer-free nanodevices.

Robust Angular Anisotropy of Circularly Polarized Luminescence from a Single Twisted-Bipolar Polymeric Microsphere.

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 glum 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 glum 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.

Signal and noise analysis for chiral structured illumination microscopy.

Recently, chiral structured illumination microscopy has been proposed to image fluorescent chiral domains at sub-wavelength resolution. Chiral structured illumination microscopy is based on the combination of structured illumination microscopy, fluorescence-detected circular dichroism, and optical chirality engineering. Since circular dichroism of natural chiral molecules is typically weak, the differential fluorescence is also weak and can be easily buried by the noise, hampering the fidelity of the reconstructed images. In this work, we systematically study the impact of the noise on the quality and resolution of chiral domain images obtained by chiral SIM. We analytically describe the signal-to-noise ratio of the reconstructed chiral SIM image in the Fourier domain and verify our theoretical calculations with numerical demonstrations. Accordingly, we discuss the feasibility of chiral SIM in different experimental scenarios and propose possible strategies to enhance the signal-to-noise ratio for samples with weak circular dichroism.

Structured illumination microscopy for simultaneous imaging of achiral and chiral domains.

We propose double structured illumination microscopy (SIM) method, which enables simultaneous imaging of achiral and chiral domains at sub-wavelength resolution. In double SIM, the illumination field is spatially structured both in the intensity and optical chirality so that moiré effects can be concurrently generated on the achiral and chiral fluorescent domains of a sample. This allows for down-modulating the high spatial frequency of both domains at the same time and thus provides sub-wavelength details after image reconstruction. We introduce the working principle of double SIM and theoretically demonstrate the feasibility of this method using different kinds of synthetic samples.

Generation of optical chirality patterns with plane waves, evanescent waves and surface plasmon waves.

We systematically investigate the generation of optical chirality patterns by applying the superposition of two waves in three scenarios, namely free-space plane waves, evanescent waves of totally reflected light at dielectric interface and propagating surface plasmon waves on a metallic surface. In each scenario, the general analytical solution of the optical chirality pattern is derived for different polarization states and propagating directions of the two waves. The analytical solutions are verified by numerical simulations. Spatially structured optical chirality patterns can be generated in all scenarios if the incident polarization states and propagation directions are correctly chosen. Optical chirality enhancement can be obtained from the constructive interference of free-space circularly polarized light or enhanced evanescent waves of totally reflected light. Surface plasmon waves do not provide enhanced optical chirality unless the near-field intensity enhancement is sufficiently high. The structured optical chirality patterns may find applications in chirality sorting, chiral imaging and circular dichroism spectroscopy.

Modal Symmetry Controlled Second-Harmonic Generation by Propagating Plasmons.

A new concept for second-harmonic generation (SHG) in an optical nanocircuit is proposed. We demonstrate both theoretically and experimentally that the symmetry of an optical mode alone is sufficient to allow SHG even in centro-symmetric structures made of centro-symmetric material. The concept is realized using a plasmonic two-wire transmission-line (TWTL), which simultaneously supports a symmetric and an antisymmetric mode. We first confirm that emission of second-harmonic light into the symmetric mode of the waveguide is symmetry-allowed when the fundamental excited waveguide modes are either purely symmetric or antisymmetric. We further switch the emission into the antisymmetric mode when a controlled mixture of the fundamental modes is excited simultaneously. Our results open up a new degree of freedom into the designs of nonlinear optical components and should pave a new avenue toward multifunctional nanophotonic circuitry.

Designable Spectrometer-Free Index Sensing Using Plasmonic Doppler Gratings.

Typical nanoparticle-based plasmonic index sensors detect the spectral shift of localized surface plasmon resonance (LSPR) upon the change of the environmental index. Therefore, they require broadband illumination and spectrometers. The sensitivity and flexibility of nanoparticle-based index sensors are usually limited because LSPR peaks are usually broad and the spectral position cannot be freely designed. Here, we present a fully designable index sensing platform using plasmonic Doppler gratings (PDGs), which provide broadband and azimuthal angle dependent grating periodicity. Different from LSPR sensors, PDG index sensors are based on the momentum matching between photons and surface plasmons via the lattice momentum of the grating. Therefore, the index change is translated into the variation of the in-plane azimuthal angle for photon-to-plasmon coupling, which manifests as directly observable dark bands in the reflection image. The PDG can be freely designed to optimally match the range of index variation for specific applications. In this work, we demonstrate PDG index sensors for large (n = 1.00-1.52) and small index variations (n = 1.3330-1.3650). The tiny and nonlinear index change of the water-ethanol mixture has been clearly observed and accurately quantified. Since the PDG is a dispersive device, it enables on-site and single-color index sensing without a spectrometer and provides a promising spectroscopic platform for on-chip analytical applications.

Photoluminescence-Driven Broadband Transmitting Directional Optical Nanoantennas.

Optical nanoantennas mediate near and far optical fields. Operating a directional nanoantenna in transmitting mode is challenging because the antenna needs to be driven by a nanosized optical frequency generator, which must work at the antenna's resonance frequency and be precisely attached to the antenna's feed with correct polarization. Quantum emitters have been used as optical nanogenerators, but their precise positioning relative to the nanoantenna is technically challenging, setting up a barrier to the practical implementation. One unique source to drive nanoantenna is the photoluminescence from the material of the nanoantenna because the high operational frequency of the antenna reaches the regime for the electronic transitions in matter. Here, we exploit plasmon-modulated photoluminescence (PMPL) as an effective optical source to drive directional nanoantennas. We experimentally realize two technically challenging theoretical proposals, namely, an optical nanospectrometer based on Yagi-Uda nanoantennas and tunable broadband directional emission from log-periodic nanoantennas. Using photoluminescence from the nanoantenna as an optical source promotes practical implementation of transmitting optical nanoantennas.

Probing the acoustic vibrations of complex-shaped metal nanoparticles with four-wave mixing.

We probe the acoustic vibrations of silver nanoprisms and gold nano-octahedrons in aqueous solution with four-wave mixing. The nonlinear optical response shows two acoustic vibrational modes: an in-plane mode of nanoprisms with vertexial expansion and contraction; an extensional mode of nano-octahedrons with longitudinal expansion and transverse contraction. The particles were also analyzed with electron microscopy and the acoustic resonance frequencies were then calculated by the finite element analysis, showing good agreement with experimental observations. The experimental mode frequencies also fit with theoretical approximations, which show an inverse dependence of the mode frequency on the edge length, for both nanoprisms and nano-octahedrons. This technique is promising for in situ monitoring of colloidal growth.

Synthesis and Evaluation of Aminothiazole-Paeonol Derivatives as Potential Anticancer Agents.

In this study, novel aminothiazole-paeonol derivatives were synthesized and characterized using ¹H-NMR, (13)C-NMR, IR, mass spectroscopy, and high performance liquid chromatography. All the new synthesized compounds were evaluated according to their anticancer effect on seven cancer cell lines. The experimental results indicated that these compounds possess high anticancer potential regarding human gastric adenocarcinoma (AGS cells) and human colorectal adenocarcinoma (HT-29 cells). Among these compounds, N-[4-(2-hydroxy-4-methoxyphenyl)thiazol-2-yl]-4-methoxybenzenesulfonamide (13c) had the most potent inhibitory activity, with IC50 values of 4.0 µM to AGS, 4.4 µM to HT-29 cells and 5.8 µM to HeLa cells. The 4-fluoro-N-[4-(2-hydroxy-4-methoxyphenyl)thiazol-2-yl]benzenesulfonamide (13d) was the second potent compound, showing IC50 values of 7.2, 11.2 and 13.8 µM to AGS , HT-29 and HeLa cells, respectively. These compounds are superior to 5-fluorouracil (5-FU) for relatively higher potency against AGS and HT-29 human cancer cell lines along with lower cytotoxicity to fibroblasts. Novel aminothiazole-paeonol derivatives in this work might be a series of promising lead compounds to develop anticancer agents for treating gastrointestinal adenocarcinoma.

Facet-Dependent and Light-Assisted Efficient Hydrogen Evolution from Ammonia Borane Using Gold-Palladium Core-Shell Nanocatalysts.

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.

Selective trapping or rotation of isotropic dielectric microparticles by optical near field in a plasmonic archimedes spiral.

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.

Mode conversion in high-definition plasmonic optical nanocircuits.

Symmetric and antisymmetric guided modes on a plasmonic two-wire transmission line have distinct properties and are suitable for different circuit functions. Being able to locally convert the guided modes is important for realizing multifunctional optical nanocircuits. Here, we experimentally demonstrate successful local conversion between the symmetric and the antisymmetric modes in a single-crystalline gold plasmonic nanocircuit with an optimally designed mode converter for optical signals at 194.2 THz. Mode conversion may find applications in controlling nanoscale light-matter interaction.

Slant-gap plasmonic nanoantennas for optical chirality engineering and circular dichroism enhancement.

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.

Transport and trapping in two-dimensional nanoscale plasmonic optical lattice.

We report the transport and trapping behavior of 100 and 500 nm diameter nanospheres in a plasmon-enhanced two-dimensional optical lattice. An optical potential is created by a two-dimensional square lattice of gold nanostructures, illuminated by a Gaussian beam to excite plasmon resonance. The nanoparticles can be guided, trapped, and arranged using this optical potential. Stacking of 500 nm nanospheres into a predominantly hexagonal closed pack crystalline structure under such a potential is also reported.

Room-temperature quantum nanoplasmonic coherent perfect absorption.

Light-matter superposition states obtained via strong coupling play a decisive role in quantum information processing, but the deleterious effects of material dissipation and environment-induced decoherence inevitably destroy coherent light-matter polaritons over time. Here, we propose the use of coherent perfect absorption under near-field driving to prepare and protect the polaritonic states of a single quantum emitter interacting with a plasmonic nanocavity at room temperature. Our scheme of quantum nanoplasmonic coherent perfect absorption leverages an inherent frequency specificity to selectively initialize the coupled system in a chosen plasmon-emitter dressed state, while the coherent, unidirectional and non-perturbing near-field energy transfer from a proximal plasmonic waveguide can in principle render the dressed state robust against dynamic dissipation under ambient conditions. Our study establishes a previously unexplored paradigm for quantum state preparation and coherence preservation in plasmonic cavity quantum electrodynamics, offering compelling prospects for elevating quantum nanophotonic technologies to ambient temperatures.