Chiral light-matter interactions in molecular semiconductors

Chirality refers to the structural property of an object that cannot be superposed onto its mirror image. The existence of chirality in nature is universal, ranging from molecules at the nanoscale to gastropod shells at the macroscale. Light can be chiral as well. Circularly polarized light with opposite helicity has its electric field vector rotating clockwise or counterclockwise during propagation. Chiral light-matter interactions are widely used in molecule detection, optical communication and quantum information processing. In this talk, I will discuss how to engineer the chiral light-matter interaction based on metamaterials and nano photonic structures towards novel imaging and sensing applications. I will first present a new concept of chiral metamirrors, which can achieve near-perfect reflection of designated circularly polarized light without reversing its handedness, yet complete absorption of the other polarization state [1]. Such a metamaterial can be used for polarimetric imaging to extract the polarization information of light [2]. Recently, we have applied the deep learning approach to accelerate the design of chiral metamaterials with prescribed chiroptical responses [3]. Finally, I will discuss the generation of chiral hotspots in silicon nanocube dimers that can amplify circular dichroism signals by one order of magnitude [4]. Our findings would lead to integrated devices for circular dichroism spectroscopy, enantioselective sensing, sorting and synthesis.

Over the last two decades, nanophotonics, including plasmonics and metamaterials, have promised compelling opportunities for exotic control over light-matter interactions. The strong chiral light-matter interaction is a representative example. Three-dimensional (3D) chirality has existed naturally only in organic molecules and bio-organisms, but a negligible chiroptic effect was attained with these naturally occurring materials because of their small absorption cross sections. However, inspired by biological chirality, nanophotonic chiral materials have greatly expanded the design space of accessible chiroptic effects (e.g., pushing the chiral light-matter interaction to an exceptional regime, such as a broad-band circular polarizer, negative refractive index, and sensitive chiral sensing). Nevertheless, it is still a challenge to achieve precisely defined and dynamically reconfigurable chiral morphologies that further increase the chiroptic effect. Biological systems continue to inspire approaches to the design and synthesis of precisely defined 3D nanostructures. In particular, a living organism can program the evolutionary pathway of highly complexed 3D chiral morphology precisely from the molecular scale to the macroscopic scale while simultaneously enabling dynamic reconfiguration of their chirality. What if we could harness the power of biological selectivity and evolutionary capability in synthesizing chiral plasmonic materials? We envisioned that platform technology mimicking biological principles would enable control of 3D chiral structures for effective plasmonic interactions with polarized light and further impart the concept of time-dependent evolution (3D + 1D = 4D) to bring about responsive and dynamic changes in chiral plasmonics. In this Account, we review our efforts to develop the biomolecule-based synthesis of 3D chiral plasmonic materials and share the vision that as in biological systems, chirality can be programmed at the molecular level and hierarchically transferred at multiple scales to develop macroscopic chirality. Accompanied by a biomimetic time-dependent chirality of singular plasmonic nanometals, we also summarize recent achievements in the chemistry and nanophotonics communities pursuing 4D plasmonics that are closely related to our research. The biomimetic and bioinspired approaches discussed in this Account will provide new synthetic insights into implementing chiral nanomaterials and extend the range of accessible nanophotonic design. We hope that the molecular encoding approach will be useful to achieve dynamic light-matter interactions at unprecedented dimensions, time scales, and chirality.

Chiral framework materials offer a promising platform for exploring circularly polarized lasing. However, the creation of chirality in current optical gain framework materials relies on the chirality transfer, which suffers from weak chiral light-matter interactions and thus limits the dissymmetry factors of circularly polarized laser emission. Here, we propose to synthesize homochiral metal-organic frameworks (MOF) from chiral optical gain molecules to enhance chiral light-matter interactions, enabling circularly polarized lasing with large dissymmetry factors. The MOFs are grown controllably into 1D microcrystals to function as Fabry-Pérot cavities providing optical feedback for laser oscillations. In addition, the chiral optical gain molecules in the frameworks exhibit high luminescence efficiencies of ∼88% because the rigid frameworks effectively suppress nonradiative decay, resulting in low-threshold lasing. More importantly, the homochiral optical gain frameworks can enhance chiral light-matter interactions, which allows for circularly polarized laser emission with dissymmetry factors larger than 1.0. Our work establishes a homochiral framework material platform for exploring high-performance circularly polarized lasing.

Molecular chirality is represented as broken mirror symmetry in the structural orientation of constituent atoms and plays a pivotal role at every scale of nature. Since the discovery of the chiroptic property of chiral molecules, the characterization of molecular chirality is important in the fields of biology, physics, and chemistry. Over the centuries, the field of optical chiral sensing was based on chiral light–matter interactions between chiral molecules and polarized light. Starting from simple optics-based sensing, the utilization of plasmonic materials that could control local chiral light–matter interactions by squeezing light into molecules successfully facilitated chiral sensing into noninvasive, ultrasensitive, and accurate detection. In this Review, the importance of plasmonic materials and their engineering in chiral sensing are discussed based on the principle of chiral light–matter interactions and the theory of optical chirality and chiral perturbation; thus, this Review can serve as a milestone for the proper design and utilization of plasmonic nanostructures for improved chiral sensing.

Detecting the chirality of molecules is of great importance in optics, biomedicine, and materials science. In chiroptical spectroscopy, it's crucial to achieve strong chiroptical signals with a minimal number of chiral molecules. The molecular chiroptical signals, however, are typically weak for chiral molecular sensing in conventional circular dichroism using photonic spin angular momentum, even in the presence of a large number of chiral molecules (micromoles to millimoles). Here, by involving chiral light-matter interaction with photonic orbital angular momentum, we demonstrate strong chiroptical responses that reflect the molecular chirality in a single chiral nanoassembly. We experimentally present the helical dichroism spectra of chiral nanoassemblies synthesized from L/D-cystines, consistent with electromagnetic simulations. The asymmetry factors in the fundamental wavelength and photoluminescence emission reach values of 0.53 and 1.18, respectively, exceeding those observed in the circular dichroism mechanism. To improve the dimensions of helical dichroism spectroscopy, we analyze helical dichroism in wavelength domain, polarization domain, and momentum space. Our findings not only expand the methods for trace chiral molecular sensing but also provide insights into chiral light-matter interactions.

The identification and separation of chiral substances are of importance in the biological, chemical, and pharmaceutical industries. Here, we demonstrate that a focused circularly polarized vortex beam can, in the focal plane, selectively trap and rotate chiral dipolar particles via radial and azimuthal optical forces. The handedness and topological charge of the incident beam have strong influence on identifying and separating behavior: left- and right-handed circular polarizations lead to opposite effects on the particle of trapping and rotating, while the sign of topological charge will change the particle's rotation direction. Such effects are a direct result of the handedness and topological charge manifesting themselves in the directions of the spin angular momentum (SAM) and Poynting vector. The research provides insight into the chiral light-matter interaction and may find potential application in the identification and separation of chiral nanoparticles.

The interaction of circularly polarized light with matter is the basis for molecular circular dichroism spectroscopy, optical spin manipulation, and optical torques. However, chiroptical effects are usually hampered by weak chiral light-matter interaction. Nanophotonic structures can enhance optical intensity to boost interactions, but magnifying chiral effects requires that the near field remains chiral in the process. Here, we propose the conditions, limits and guidelines for enhancing different chiroptical effects near achiral metasurfaces with maximum chirality of the evanescent fields. We illustrate these conditions with arrays of metal and dielectric nanodisks and decompose their distinct electromagnetic metrics into propagating and evanescent Fourier orders. We prove that chirality metrics like circular dichroism and the degree of circular polarization, which go hand-in-hand in the far field for propagating plane waves, are incompatible in the evanescent near field. As a result, a nanostructure cannot be universally optimal for different chirality metrics and therefore applications. For example, arrays tailored for enhanced spin excitation with spatially uniform circular polarization destroy circular dichroism. Conversely, we predict a limit of maximum attainable circular dichroism in highly evanescent Fourier orders through a simple relation with the evanescent wavevector and polarization. We demonstrate that silicon nanodisk arrays can enhance chiral effects within these constraints. Our results define the limits on the ability of nanophotonic platforms to enhance different chiral light-matter interactions simultaneously. Our work provides design rules for diverse chiroptical applications such as molecular spectroscopy, information technology and optical nanomanipulation.

Surface plasmon polaritons (SPPs) carry transverse optical spin within the evanescent field, which has enabled the demonstration of various chiral light–matter interactions in classical and quantum systems. To achieve high spin selectivity in the interactions, the elliptical polarization of the evanescent field should be made circular, but the engineering principle of the degree of circular polarization (DOCP) of SPPs has been lacking. In this study, we theoretically and numerically investigate the scaling behavior of the DOCP of the SPP field with respect to the modal effective refractive index (neff). The DOCP of the SPP field exhibits power-law scalability to the effective refractive index in the one-dimensional (1D) layered system regardless of the material, structural geometry, and excitation wavelength. The power-law scalability is also confirmed in two-dimensional (2D) waveguide structures for in-plane and out-of-plane SPP fields, but the scaling exponents vary depending on the distance from the waveguide boundaries by the reduced symmetry of the given system. Due to Lorentz reciprocity, the power-law scalability can be extended to the coupling directionality of chiral emitters toward the plasmonic waveguide. To this end, we propose a chiral photonic platform for enhanced light–valley interaction, which utilizes simultaneous enhancement of the DOCP and coupling directionality. An incident SPP can excite a chiral emitter with high spin selectivity that unidirectionally couples the emitted light into the plasmonic waveguide, depending on the valley polarization of excitons in 2D materials. Our work provides a ground rule for designing chiral nanophotonic systems and paves the way for the exploration of scale-free phenomena of electromagnetic waves.

We investigate how the near-field enhancement of self-similar nanolenses, made of three plasmonic nanospheres with decreasing sizes and separations, is affected by quantum corrections in the optical response of the metal and by fabrication imperfections related to the positioning of the spheres in the nanolens. In particular, we integrate mesoscopic phenomena, such as electron spill-in and -out and surface-enabled Landau damping, via the surface-response formalism, focusing particularly on the role of spill-out in alkali metals. In addition, we take realistic imperfections in the nanofabrication process into account, through numerical averaging of both far- and near-field spectra for large collections of nanolenses. Statistical analysis of hundreds of trimers shows that inevitable deviations from the perfectly aligned chain only slightly, if at all, impair the field enhancement, as long as the average misplacement is kept within 1 nm from the ideal situation. Wishing to explore whether such imperfections can be harvested for practical applications, we probe the potential for triggering chiral response. Our results verify that imperfect nanolenses can display considerable light-induced optical activity and circular dichroism, while providing a means to manipulate the optical chirality density. This highlights how promising the nanolensing effect is for chiral light–matter interactions. Nonetheless, we emphasize that quantification of chiral light–matter interactions can be largely affected by mesoscopic phenomena, which cannot be ignored when near-field quantities like optical chirality density are investigated.

Circularly polarized (CP) lasers hold tremendous potential for advancing spin information communication and display technologies. Organic materials are emerging candidates for high-performance CP lasers because of their abundant chiral structures and excellent gain characteristics. However, their dissymmetry factor (glum) in CP emission is typically low due to the weak chiral light matter interactions. Here, we presented an effective approach to significantly amplifying glum by leveraging the intrinsic 2D-chiroptical response of an anisotropic organic supramolecular crystal. The organic complex microcrystal was designed to exhibit large 2D-chiroptical activities through strong coupling interactions between their remarkable linear birefringence (LB) and high degree of fluorescence linear polarization. Such 2D-chiroptical response can be further enhanced by the stimulated emission resulted from an increased degree of linear polarization, yielding a nearly pure CP laser with an exceptionally high glum of up to 1.78. Moreover, exploiting the extreme susceptibility of LB to temperature, we demonstrate a prototype of temperature-controlled chiroptical switches. These findings offer valuable insights for harnessing organic crystals to facilitate the development of high-performance CP lasers and other chiroptical devices.

Monolayer transition metal dichalcogenides feature tightly bound bright excitons at the degenerate valleys, where electron-hole Coulomb exchange interaction strongly couples the valley pseudospin to the momentum of the exciton. Placed on a periodically structured dielectric substrate, the spatial modulation of the Coulomb interaction leads to the formation of exciton Bloch states with real-space valley pseudospin texture displayed in a mesoscopic supercell. We find this spatial valley texture in the exciton Bloch function is pattern locked to the propagation direction, enabling nano-optical excitation of directional exciton flow through the valley selection rule. The left-right directionality of the injected exciton current is controlled by the circular polarization of excitation, while the angular directionality is controlled by the excitation location, exhibiting a vortex pattern in a supercell. The phenomenon is reminiscent of the chiral light-matter interaction in nanophotonics structures, with the role of the guided electromagnetic wave now replaced by the valley-orbit coupled exciton Bloch wave in a uniform monolayer, which points to new excitonic devices with nonreciprocal functionalities.

Distinguishing left- and right-handed molecules is challenging, especially on ultrafast time scale. Traditionally one uses a chiral reagent, an object of known handedness, to determine the unknown handedness of a chiral molecule. In optics, one uses the spatial helix formed by circularly polarized light as a “chiral photonic reagent”. However, in optical domain the pitch of this

Chirality-dependent photocatalysis is an emerging domain that leverages unique chiral light-matter interactions for enabling asymmetric catalysis driven by spin polarization induced by circularly polarized light selection. Herein, we synthesize chiral inorganic polar BaTiO3/BaCO3 nanohybrids for asymmetric photocatalysis via a hydrothermal method employing chiral glucose as a structural inducer. When excited by opposite circularly polarized light, the same material exhibits significant asymmetric catalysis, while enantiomers present an opposite polarization preference. More importantly, the preferred circularly polarized light undergoes reversal with reversal of the CD signal. Systematic experimental results demonstrate that more photogenerated carriers are generated in chiral semiconductors under suitable circularly polarized light irradiation, including more spin-polarized electrons, which inhibits the recombination of electron-hole pairs and promotes the activation of oxygen molecules into reactive oxygen species, thus inducing this asymmetric photocatalytic feature. This study provides valuable insights for the development of highly efficient polarization-sensitive chiral perovskite nanostructures as promising candidates for next-generation, multifunctional chiral device applications.

We report a theoretical modeling on the excitation of chiro-optical activity in chiral assemblies comprising of dielectric nanoparticles using a semianalytical method based on coupled dipole approximation. In stark contrast to plasmonic counterparts where electric dipolar coupling dominates chiro-optical response, our analysis reveals a magnetic-dominated response, which originates from the dynamic electromagnetic coupling between the magnetic dipole moments of the individual high-index dielectric nanoparticles. The calculated circular dichroism response practically remains insensitive to interparticle spacing but shows strong dependence on the size of nanoparticle and refractive index, in close agreement with numerical simulations. Such a chiral assembly represents a novel material platform where individual achiral dielectric nanoparticles with strong magnetic resonances can be exploited as building blocks for engineering new type of chiral light–matter interaction, and being low in light absorption loss, this could be promising for applications in nanophotonics.

Unified framework for enhancing chiral light-matter interactions