Chiral light-matter interactions for imaging and sensing (Conference Presentation)

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.

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.

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.

Circular dichroism (CD) of chiral metamaterials is of significant interest for bio-sensing and molecular chemistry applications. In this study, using the gammadion shape as an example, the CD effect of gammadion-shaped chiral metamaterials is investigated. We view the gammadion as four Γ-shaped structures. The CD effect of the gammadion is induced by the conductive and magneto-inductive coupling between the weak and strong magnetic fields of the Γ-shaped structures. A large CD effect can be achieved because the magnetic fields excited by the conductive and magneto-inductive coupling show the same and opposing directions for right- and left-handed circular-polarized waves, respectively. This allows analysis of the origin of plasmonic modes in the CD spectrum. We can change the CD effect by changing the conductive and magneto-inductive coupling of the magnetic fields. The CD properties can be tuned by changing either the number of Γ-shaped structures or the layer spacing. These results may guide the design of chiral metamaterials at terahertz frequencies for achieving large CD effects. Furthermore, this approach can be applied to other complex planar structures to gain further insight on the origin of CD modes.

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.

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.

Chirality is a property which is widely observed in nature and refers to the characteristic that an object cannot be superimposed on its mirror image. Recently, chiral solution-processable semiconductors have seen a surge of interest for their potential applications in emerging photonic, optoelectronic and spintronic technologies [1]. Yet, the underlying chiral light-matter interactions, especially in the excited state, which lead to spin and light polarization remain poorly understood [2]. Here, we present our preliminary results on employing transient chiroptical spectroscopy to understand the consequences of morphological (hierarchical) chirality for charge, spin and light polarization. We compare achiral chromophores in solution and a solid-state matrix with their arrangement into chiral twisted molecular crystal films with chiral domains and discuss the complex photophysics we observe [3]. By studying chiral light-matter interactions transiently and with high sensitivity we hope to aid in understanding the microscopic origin of chiral-induced spin-selectivity (CISS) observations and other mechanistic approaches that could enable efficient spin and light polarization control using cheap solution- processable semiconductors.

Two series of sequential poly(Lys-X) (X: Gly, βAla, and ɛAhx in series A; Gly, Ala, Leu and Phe in series B) have been synthesized. On the chiral interaction between cationic polypeptides and methyl orange (MO), the effects of the distance (series A) and of the hydrophobic side chains (series B) were examined by means of the absorption and induced circular dichroism (CD) spectroscopies. Dichroic bands associated with the blue shifted absorption peaks or shoulders of MO in the visible wavelength region were observed by complex formation between the polypeptides and the dye. The intensity of the induced CD was affected by the concentration of the complexes and time after preparing the complex solutions, suggesting the formation of the intermolecular aggregation in some instances. When MO molecules bound to lysine residues are apart from each other, the aggregation of the complexes is not marked. Roughly, the intensity of the induced CD decreases with increasing distance between the intramolecular lysine residues in series A polypeptides. When the hydrophobicity of the side chains is increased, the induced CD spectra of the series B polypeptide-MO complexes exhibits the inversion of the sign of the induced CD extrema.

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.

The detection and discrimination of molecular chirality are essential for the advancement of pharmaceutical and biological applications. While nanophotonic platforms offer a route to enhance chiral light-matter interactions, existing device concepts for chiral sensing remain heuristic, resulting in limited chiral enhancement and control over chiral hotspot placement within nanostructures. Here, we introduce an inverse design framework that directly optimizes superchiral near fields in photonic nanostructures and demonstrate its powerful opportunities for enantioselective analysis. We first show that freeform achiral metasurfaces can be optimized to achieve an 820-fold chiral density enhancement with fully customizable chiral hotspot placement for direct molecular interaction. We then leverage this platform to demonstrate ultrasensitive detection of chiral analytes and quantitative readout of the chiral concentration and enantiomeric excess in chiral mixtures. Our framework offers a generic route to realizing superchiral nanophotonic platforms compatible with diverse spin-based photonic materials for valleytronics, chiral emission control, and topological photonics.

Chiral imaging encryption, which encodes information in meta‐atoms revealed under specific polarization states, is a promising security technology. However, conventional methods rely on external light sources and offer only a single polarization channel, which hinders miniaturization and integration. Herein, we demonstrate an intelligent metasurface based on vanadium dioxide (VO 2 ) phase‐change material (PCM) that overcomes these limitations. The metasurface generates linearly polarized thermal radiation with a linear dichroism (LD) of 0.71 in the insulating VO 2 phase and chiral emission with a circular dichroism (CD) of 0.58 in the metallic VO 2 phase, enabling dynamic switching between polarization states via temperature control. In addition, the LD and CD can be broadly tuned by modifying geometric parameters. Based on this mechanism, we designed a digitally encoded metasurface composed of diverse meta‐atoms, which conceals specific patterns that are only revealed under the proper combination of operating temperature and polarization state, thus achieving image dual‐encryption. Furthermore, the metasurface could display distinct images with low crosstalk under non‐orthogonal polarization states, which stems from the different capabilities of geometric parameters to modulate elliptically polarized radiation. Our work establishes a new paradigm for eco‐friendly optical devices, providing key theoretical and technical support for intelligent thermal radiation modulation.

The measurement of circular dichroism (CD) has widely been exploited to distinguish the different enantiomers of chiral structures. It has been applied to natural materials (e.g. molecules) as well as to artificial materials (e.g. nanophotonic structures). However, especially for chiral molecules the signal level is very low and increasing the signal-to-noise ratio is of paramount importance to either shorten the necessary measurement time or to lower the minimum detectable molecule concentration. As one solution to this problem, we propose here to use quantum states of light in CD sensing to reduce the noise below the shot noise limit that is encountered when using coherent states of light. Through a multi-parameter estimation approach, we identify the ultimate quantum limit to precision of CD sensing, allowing for general schemes including additional ancillary modes. We show that the ultimate quantum limit can be achieved by various optimal schemes. It includes not only Fock state input in direct sensing configuration but also twin-beam input in ancilla-assisted sensing configuration, for both of which photon number resolving detection needs to be performed as the optimal measurement setting. These optimal schemes offer a significant quantum enhancement even in the presence of additional system loss. The optimality of a practical scheme using a twin-beam state in direct sensing configuration is also investigated in details as a nearly optimal scheme for CD sensing when the actual CD signal is very small. Alternative schemes involving single-photon sources and detectors are also proposed. This work paves the way for further investigations of quantum metrological techniques in chirality sensing.

Coherently manipulating single photons in nanophotonic structures with unidirectional propagation is one of the central goals for integrated quantum information processing. Photonic devices constructed by a single atom coupled to a whispering-gallery-mode microresonator (WGMM) with nonideal chiral photon-atom interactions inevitably induce undesired photon scattering. Here, an external scatterer is introduced to the WGMM to cancel the reflection of signal photons by an atom due to nonideal chiral interactions. By properly tuning the positions of the scatterer, destructive and constructive interferences between reflected photons of different pathways are utilized to control the reflection properties of single incident photons. The results show that the reflection probabilities can be suppressed by applying the interplay between chirality and backscattering. Constructing perfect destructive interferences directly leads to unidirectional propagation even when the photon-atom interactions are not ideal. Because the amplitudes of the reflected photons produced by the scatterer can be enhanced to meet requirements of perfect destructive interfering processes, unidirectional propagation is preserved against dissipations.

Trace detection of chiral molecules, which is of great significance in chemical, biological, medical and pharmaceutical sciences, requires microscopic techniques at the single-particle or single-molecule level. Although ensemble experiments show that the circular dichroism of chiral molecules can be amplified by plasmonic nanocrystals, trace detection of small chiral molecules remains challenging due to weak signals that are far below the detection limit. Herein, we demonstrate trace detection of chiral J-aggregated molecules adsorbed on individual Au nanorods (NRs) using single-particle circular differential scattering (CDS) spectroscopy. Through measuring the single-particle CDS spectra, we identified dip-peak bisignatures and further determined the chirality by matching them with calculations modelled with chiral media. We therefore find that plasmonic nanocrystals can dramatically amplify the circular dichroism of strongly coupled molecules to a detectable level so that the detection limit is as low as 3.9 × 103 molecules on an individual plasmonic nanoparticle, whereas 2.5 × 1012 molecules free in solution are barely detectable using a commercial circular dichroism instrument, suggesting a significant amplification factor of 108. Our method provides a promising strategy with a high amplification factor, shedding light on the trace detection of chiral molecules using optical microscopic methods.

Chiral molecules and their interactions are critical in a variety of chemical and biological processes. Circular dichroism (CD) is the most widely used optical technique to study chirality, often performed in a solution phase. However, CD has low-efficiency on the order of 0.01–1%. Therefore, there is a growing need to develop high-efficiency chiroptical techniques, especially in gas-phase, to gain background-free in-depth insight into chiral interactions. By using mass spectrometry and strong-field ionization of limonene with elliptically polarized light, we demonstrate an efficient chiral discrimination method that produces a chiral signal of one to two orders of magnitude higher than the conventional CD. The chiral response exhibits a strong dependence on wavelength in the range of 1,300–2,400 nm, where the relative abundance of the ion yields alternates between the two enantiomers. The origin of enhanced enantio-sensitivity in intense laser fields is attributed to two mechanisms that rely on the recollision dynamics in a chiral system: (1) the excited ionic state dynamics mediated either by the laser field or by the recollision process, and (2) non-dipole effects that alter the electron’s trajectories. Our results can serve as a benchmark for testing and developing theoretical tools involving non-dipole effects in strong-field ionization of molecules.