Strong Light-matter Coupling Regime Research Articles

FMO-LC-TDDFTB method for excited states of large molecular assemblies in the strong light-matter coupling regime.

We present a new methodology to calculate the strong light-matter coupling between photonic modes in microcavities and large molecular aggregates that consist of hundreds of molecular fragments. To this end, we combine our fragment molecular orbital long-range corrected time-dependent density functional tight-binding methodology with a generalized Tavis-Cummings Hamiltonian. We employ an excitonic Hamiltonian, which is built from a quasi-diabatic basis that is constructed from locally excited and charge-transfer states of all molecular fragments. To calculate polaritonic states, we extend our quasi-diabatic basis to include photonic states of a microcavity and derive and implement the couplings between the locally excited states and the cavity states and built a Tavis-Cummings Hamiltonian that incorporates the intermolecular excitonic couplings. Subsequently, we demonstrate the capability of our methodology by simulating the influence of the electric field polarization on the polaritonic spectra for a tetracene aggregate of 125 monomers. Furthermore, we investigate the dependence of the splitting of the upper and lower polaritonic branches on the system size by comparing the spectra of five different tetracene clusters. In addition, we investigate the polariton dispersion of a large tetracene aggregate for electric field polarizations in the x, y, and z directions. Our new methodology can facilitate the future study of exciton dynamics in complex molecular systems, which consist of up to hundreds of molecules that are influenced by strong light-matter coupling to microcavities.

Exact factorization of the photon-electron-nuclear wavefunction: Formulation and coupled-trajectory dynamics.

We employ the exact-factorization formalism to study the coupled dynamics of photons, electrons, and nuclei at the quantum mechanical level, proposing illustrative examples of model situations of nonadiabatic dynamics and spontaneous emission of electron-nuclear systems in the regime of strong light-matter coupling. We make a particular choice of factorization for such a multi-component system, where the full wavefunction is factored as a conditional electronic amplitude and a marginal photon-nuclear amplitude. Then, we apply the coupled-trajectory mixed quantum-classical (CTMQC) algorithm to perform trajectory-based simulations, by treating photonic and nuclear degrees of freedom on equal footing in terms of classical-like trajectories. The analysis of the time-dependent potentials of the theory along with the assessment of the performance of CTMQC allows us to point out some limitations of the current approximations used in CTMQC. Meanwhile, comparing CTMQC with other trajectory-based algorithms, namely multi-trajectory Ehrenfest and Tully surface hopping, demonstrates the better quality of CTMQC predictions.

Metasurface of Strongly Coupled Excitons and Nanoplasmonic Arrays.

Metasurfaces allow light to be manipulated at the nanoscale. Integrating metasurfaces with transition metal dichalcogenide monolayers provides additional functionality to ultrathin optics, including tunable optical properties with enhanced light-matter interactions. In this work, we demonstrate the realization of a polaritonic metasurface utilizing the sizable light-matter coupling of excitons in monolayer WSe2 and the collective lattice resonances of nanoplasmonic gold arrays. We developed a novel fabrication method to integrate gold nanodisk arrays in hexagonal boron nitride and thus simultaneously ensure spectrally narrow exciton transitions and their immediate proximity to the near-field of array surface lattice resonances. In the regime of strong light-matter coupling, the resulting van der Waals metasurface exhibits all key characteristics of lattice polaritons, with a directional and linearly polarized far-field emission profile dictated by the underlying nanoplasmonic lattice. Our work can be straightforwardly adapted to other lattice geometries, establishing structured van der Waals metasurfaces as means to engineer polaritonic lattices.

Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime

Strong coupling between molecules and confined light modes of optical cavities to form polaritons can alter photochemistry, but the origin of this effect remains largely unknown. While theoretical models suggest a suppression of photochemistry due to the formation of new polaritonic potential energy surfaces, many of these models do not account for the energetic disorder among the molecules, which is unavoidable at ambient conditions. Here, we combine simulations and experiments to show that for an ultra-fast photochemical reaction such thermal disorder prevents the modification of the potential energy surface and that suppression is due to radiative decay of the lossy cavity modes. We also show that the excitation spectrum under strong coupling is a product of the excitation spectrum of the bare molecules and the absorption spectrum of the molecule-cavity system, suggesting that polaritons can act as gateways for channeling an excitation into a molecule, which then reacts normally. Our results therefore imply that strong coupling provides a means to tune the action spectrum of a molecule, rather than to change the reaction.

Influence of atomistic features in plasmon-exciton coupling and charge transfer driven by a single molecule in a metallic nanocavity.

When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic abinitio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.

Multiple micro-cavity vibro-polaritons formation with different vibrational bands of the methylene group

We present an experimental technique to accurately predict the formation of vibro-polaritons from a molecular polymeric film embedded in a resonant mid-infrared cavity. Using simple Fourier-transform reflectance measurement, we extract the complex dielectric function of a polyethylene film using Kramers-Kronig relations. The fitted dielectric function can be plugged into a numerical code to predict the strength and dispersion of the strong light-matter coupling regime between the quantized electromagnetic modes of a microcavity and the vibrational bands of the molecules. As a demonstration, we experimentally resolve the simultaneous formation of multiple vibro-polariton modes issued from the strong coupling of some vibrational bands of the methylene group (CH2) in a 2.5-μm-thick polyethylene film embedded in a microcavity. We measure a Rabi splitting of 6.3 THz for the stretching doublet around 87.5 THz and a Rabi splitting of 1.1 THz for the scissoring doublet around 43.7 THz, in excellent agreement with numerical predictions.

Microcavity phonoritons – a coherent optical-to-microwave interface

Optomechanical systems provide a pathway for the bidirectional optical-to-microwave interconversion in (quantum) networks. These systems can be implemented using hybrid platforms, which efficiently couple optical photons and microwaves via intermediate agents, e.g. phonons. Semiconductor exciton-polariton microcavities operating in the strong light-matter coupling regime offer enhanced coupling of near-infrared photons to GHz phonons via excitons. Furthermore, a new coherent phonon-exciton-photon quasiparticle termed phonoriton, has been theoretically predicted to emerge in microcavities, but so far has eluded observation. Here, we experimentally demonstrate phonoritons, when two exciton-polariton condensates confined in a μm-sized trap within a phonon-photon microcavity are strongly coupled to a confined phonon which is resonant with the energy separation between the condensates. We realize control of phonoritons by piezoelectrically generated phonons and resonant photons. Our findings are corroborated by quantitative models. Thus, we establish zero-dimensional phonoritons as a coherent microwave-to-optical interface.

Nonlinear self-action of ultrashort guided exciton–polariton pulses in dielectric slab coupled to 2D semiconductor

Recently reported large values of exciton–polariton nonlinearity of transition metal dichalcogenide (TMD) monolayers coupled to optically resonant structures approach the values characteristic for GaAs-based systems in the regime of strong light-matter coupling. Contrary to the latter, TMD-based polaritonic devices remain operational at ambient conditions and therefore have greater potential for practical nanophotonic applications. Here, we present the study of the nonlinear properties of Ta2O5 slab waveguide coupled to a WSe2 monolayer. We confirm that the hybridization between the waveguide mode and the exciton resonance in WSe2 gives rise to the formation of guided exciton–polaritons with Rabi splitting of 36 meV. By measuring transmission of ultrashort optical pulses through this TMD-based polaritonic waveguide, we demonstrate the strong nonlinear dependence of the output spectrum on the input pulse energy. We develop a theoretical model that shows agreement with the experimental results and gives insights into the dominating microscopic processes which determine the nonlinear pulse self-action: Coulomb exciton–exciton interaction and scattering to an incoherent excitonic reservoir. Based on the numerical simulation of nonlinear phenomena in our polariton system, we conclude that it may support a quasi-stationary solitonic regime of pulse propagation at intermediate pump energies. Our results provide an important step for the development of nonlinear on-chip polaritonic devices based on 2D semiconductors.

Low intensity saturation of an ISB transition by a mid-IR quantum cascade laser

We demonstrate that absorption saturation of a mid-infrared intersubband transition can be engineered to occur at moderate light intensities of the order of 10–20 kW cm−2 and at room temperature. The structure consists of an array of metal–semiconductor–metal patches hosting a judiciously designed 253 nm thick GaAs/AlGaAs semiconductor heterostructure. At low incident intensity, the structure operates in the strong light–matter coupling regime and exhibits two absorption peaks at wavelengths close to 8.9 μm. Saturation appears as a transition to the weak coupling regime—and therefore, to a single-peaked absorption—when increasing the incident intensity. Comparison with a coupled mode theory model explains the data and permits to infer the relevant system parameters. When the pump laser is tuned at the cavity frequency, the reflectivity decreases with increasing incident intensity. When instead the laser is tuned at the polariton frequencies, the reflectivity non-linearly increases with increasing incident intensity. At those wavelengths, the system, therefore, mimics the behavior of a saturable absorption mirror in the mid-IR range, a technology that is currently missing.

Mechanical scanning probe lithography of perovskites for fabrication of high-Q planar polaritonic cavities

Exciton–polaritons are unique quasiparticles with hybrid properties of an exciton and a photon, opening ways to realize ultrafast strongly nonlinear systems and inversion-free lasers based on Bose–Einstein polariton condensation. However, the real-world applications of polariton systems are still limited due to the temperature operation and costly fabrication techniques for both exciton materials and photon cavities. 2D perovskites represent one of the most prospective platforms for the realization of strong light-matter coupling since they support room-temperature exciton states with large oscillator strength and can simultaneously be used for fabrication of planar photon cavities with strong field localization due to the high refractive index of the material. In this work, we demonstrate the affordable mechanical scanning probe lithography method for research purposes and for the realization of room-temperature exciton–polariton systems based on 2D perovskite (PEA)2PbI4 with the Rabi splitting exceeding 200 meV. By the precise control of lithography parameters, we broadly adjust the exciton–polariton dispersion and, in particular, vary the radiative coupling of polaritonic modes to the free space. Our findings represent a versatile approach to fabrication of planar high-quality perovskite-based photonic cavities supporting the strong light-matter coupling regime for the development of on-chip all-optical active and nonlinear polaritonic devices.

Chiral discrimination in helicity-preserving Fabry-Pérot cavities

We theoretically study circular dichroism of chiral molecules embedded inside a helicity-preserving Fabry-P\'erot cavity. We find an increase of the intrinsic chiroptical response of the molecules by 2 orders of magnitude and report the first clear signature of chiral cavity polaritons upon entering the regime of strong light-matter coupling. We study a cavity design based on two dielectric photonic crystal mirrors acting, in a narrow frequency range, as efficient polarization cross-converters in transmission for one polarization and almost perfect reflectors for the other polarization. We show that a Pasteur medium hosted inside such a cavity can couple efficiently to both the outside of the cavity and to the helicity-preserving mode, inheriting an enhanced chiral character. We expect such a device to be useful in the future to design ultrasensitive chiral sensors for optics and stereochemistry.

Room-Temperature Electrical Field-Enhanced Ultrafast Switch in Organic Microcavity Polariton Condensates.

Integrated electro-optical switches are essential as one of the fundamental elements in the development of modern optoelectronics. As an architecture for photonic systems exciton polaritons, hybrid bosonic quasiparticles that possess unique properties derived from both excitons and photons, have shown much promise. For this system, we demonstrate a significant improvement of emitted intensity and condensation threshold by applying an electric field to a microcavity filled with an organic microbelt. Our theoretical investigations indicate that the electric field makes the excitons dipolar and induces an enhancement of the exciton-polariton interaction and of the polariton lifetime. Based on these electric field-induced changes, a sub-nanosecond electrical field-enhanced polariton condensate switch is realized at room temperature, providing the basis for developing an on-chip integrated photonic device in the strong light-matter coupling regime.

Resonant tunneling diodes in semiconductor microcavities: Modeling polaritonic features in the terahertz displacement current

We develop in this work a simple qualitative quantum electron transport model, in the strong light-matter coupling regime under dipole approximation, able to capture polaritonic signatures in the time-dependent electrical current. The effect of the quantized electromagnetic field in the displacement current of a resonant tunneling diode inside an optical cavity is analyzed. The original peaks of the bare electron transmission coefficient split into two new peaks due to the resonant electron-photon interaction, leading to coherent Rabi oscillations among the polaritonic states that are developed in the system in the strong coupling regime. This mimics known effects predicted by a Jaynes-Cummings model in closed systems, and shows how a full quantum treatment of electrons and electromagnetic fields may open interesting paths for engineering new THz electron devices. The computational burden involved in the multi-time measurements of THz currents is tackled by invoking a Bohmian description of the light-matter interaction. We also show that the traditional static transmission coefficient used to characterize DC quantum electron devices has to be substituted by a new displacement current coefficient in high-frequency AC scenarios.

Fabrication of high-quality PMMA/SiOx spaced planar microcavities for strong coupling of light with monolayer WS2 excitons

Exciton polaritons in atomically thin transition metal dichalcogenide crystals (monolayer TMDCs) have emerged as a promising candidate to enable topological transport, ultra-efficient laser technologies, and collective quantum phenomena such as polariton condensation and superfluidity at room temperature. However, integrating monolayer TMDCs into high-quality planar microcavities to achieve the required strong coupling between the cavity photons and the TMDC excitons (bound electron–hole pairs) has proven challenging. Previous approaches to integration had to compromise between various adverse effects on the strength of light–matter interactions in the monolayer, the cavity photon lifetime, and the lateral size of the microcavity. Here, we demonstrate a scalable approach to fabricate high-quality planar microcavities with an integrated monolayer WS2 layer-by-layer by using polymethyl methacrylate/silicon oxide (PMMA/SiOx) as a cavity spacer. Because the exciton oscillator strength is well protected against the required processing steps by the PMMA layer, the microcavities investigated in this work, which have quality factors of above 103, can operate in the strong light–matter coupling regime at room temperature. This is an important step toward fabricating wafer-scale and patterned microcavities for engineering the exciton-polariton potential landscape, which is essential for enabling many proposed technologies.

Reshaping the Jaynes-Cummings ladder with Majorana bound states

We study the optical properties of a hybrid device composed by a quantum dot (QD) resonantly coupled to a photonic mode of an optical microcavity and a Majorana nanowire: a topological superconducting segment hosting Majorana bound states (MBSs) at the opposite ends. In the regime of strong light-matter coupling, it is demonstrated that the leakage of the Majorana mode into the QD opens new optical transitions between polaritonic states formed due to hybridisation of material excitation with cavity photons, which leads to the reshaping of the Jaynes-Cummings ladder and can lead to the formation of a robust single-peak at cavity eigenfrequency in the emission spectrum. Moreover, weak satellite peaks in the low and high frequency regions are revealed for the distinct cases of highly isolated MBSs, overlapped MBSs and MBSs not well localized at the nanowire ends.

Spontaneous emission of a quantum emitter near a graphene nanodisk under strong light-matter coupling

We investigate the dynamical evolution of the spontaneous emission of a two-level quantum emitter near a graphene nanodisk. We employ the macroscopic quantum electrodynamics methodology to study the reversible population dynamics of the excited state of the quantum emitter in the non-Markovian limit. Our results indicate that the quantum-emitter--nanodisk interaction enters the strong light-matter coupling regime, as manifested in the excited-state probability where Rabi oscillations and population trapping effects are observed. The level of non-Markovianity is estimated by computing three different well-established measures and relate them to the quantum speedup due to the strong-coupling interaction of the emitter with the graphene nanodisk. Importantly, high values of the non-Markovianity and quantum speedup measures are achieved when the emitter-nanodisk interaction is strong, whereas decreasing coupling strength leads to smaller values.

Identifying Vibrations that Control Non-adiabatic Relaxation of Polaritons in Strongly Coupled Molecule-Cavity Systems.

The strong light–matter coupling regime, in which excitations of materials hybridize with excitations of confined light modes into polaritons, holds great promise in various areas of science and technology. A key aspect for all applications of polaritonic chemistry is the relaxation into the lower polaritonic states. Polariton relaxation is speculated to involve two separate processes: vibrationally assisted scattering (VAS) and radiative pumping (RP), but the driving forces underlying these two mechanisms are not fully understood. To provide mechanistic insights, we performed multiscale molecular dynamics simulations of tetracene molecules strongly coupled to the confined light modes of an optical cavity. The results suggest that both mechanisms are driven by the same molecular vibrations that induce relaxation through nonadiabatic coupling between dark states and polaritonic states. Identifying these vibrational modes provides a rationale for enhanced relaxation into the lower polariton when the cavity detuning is resonant with specific vibrational transitions.

Spontaneous Formation of Time-Periodic Vortex Cluster in Nonlinear Fluids of Light.

We demonstrate spontaneous formation of a nonlinear vortex cluster state in a microcavity exciton-polariton condensate with time-periodic sign flipping of its topological charges at the GHz scale. When optically pumped with a ring-shaped nonresonant laser, the trapped condensate experiences intricate high-order mode competition and fractures into two distinct trap levels. The resulting mode interference leads to robust condensate density beatings with periodic appearance of orderly arranged phase singularities. Our work opens new perspectives on creating structured free-evolving light, and singular optics in the strong light-matter coupling regime.

Microscopic theory of exciton and trion polaritons in doped monolayers of transition metal dichalcogenides

We study a doped transition metal dichalcogenide (TMDC) monolayer in an optical microcavity. Using the microscopic theory, we simulate spectra of quasiparticles emerging due to the interaction of material excitations and a high-finesse optical mode, providing a comprehensive analysis of optical spectra as a function of Fermi energy and predicting several modes in the strong light-matter coupling regime. In addition to exciton-polaritons and trion-polaritons, we report polaritonic modes that become bright due to the interaction of excitons with free carriers. At large doping, we reveal strongly coupled modes corresponding to excited trions that hybridize with a cavity mode. We also demonstrate that the increase of carrier concentration can change the nature of the system’s ground state from the dark to the bright one. Our results offer a unified description of polaritonic modes in a wide range of free electron densities.

Theory of Nonlinear Excitonic Response of Hybrid Organic Perovskites in the Regime of Strong Light-Matter Coupling

We present a quantitative study of the nonlinear optical response of layered perovskites placed inside planar photonic microcavities in the regime of strong light matter coupling, when excitonic and photonic modes hybridize and give rise to cavity polaritons. Two sources of nonlinearity are specified, the saturation of the excitonic transition with increase of the optical pump and Coulomb interaction between the excitons. It is demonstrated, that peculiar form of the interaction potential, specific to multilayer structure of organic perovskites, is responsible for substantial increase of the exciton binding energy and Rabi splitting with respect to conventional semiconductor systems. This results in dominant contribution of the Rabi splitting quench effect in the nonlinear optical response. Moreover, due to the tightly bound character of excitons, the density of Mott transition is essentially higher, allowing to reach extremely large polariton blueshifts of about 50 meV, which is order of magnitude higher than in conventional semiconductors.