Strong Light-matter Coupling Research Articles

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.

Inducing Strong Light-Matter Coupling and Optical Anisotropy in Monolayer MoS2 with High Refractive Index Nanowire.

Mixed-dimensional heterostructures combine the merits of materials of different dimensions; therefore, they represent an advantageous scenario for numerous technological advances. Such an approach can be exploited to tune the physical properties of two-dimensional (2D) layered materials to create unprecedented possibilities for anisotropic and high-performance photonic and optoelectronic devices. Here, we report a new strategy to engineer the light–matter interaction and symmetry of monolayer MoS2 by integrating it with one-dimensional (1D) AlGaAs nanowire (NW). Our results show that the photoluminescence (PL) intensity of MoS2 increases strongly in the mixed-dimensional structure because of electromagnetic field confinement in the 1D high refractive index semiconducting NW. Interestingly, the 1D NW breaks the 3-fold rotational symmetry of MoS2, which leads to a strong optical anisotropy of up to ∼60%. Our mixed-dimensional heterostructure-based phototransistors benefit from this and exhibit an improved optoelectronic device performance with marked anisotropic photoresponse behavior. Compared with bare MoS2 devices, our MoS2/NW devices show ∼5 times enhanced detectivity and ∼3 times higher photoresponsivity. Our results of engineering light–matter interaction and symmetry breaking provide a simple route to induce enhanced and anisotropic functionalities in 2D materials.

Prediction of Strong Transversal s(TE) Exciton-Polaritons in C60 Thin Crystalline Films.

If an exciton and a photon can change each other’s properties, indicating that the regime of their strong bond is achieved, it usually happens in standard microcavity devices, where the large overlap between the ’confined’ cavity photons and the 2D excitons enable the hybridization and the band gap opening in the parabolic photonic branch (as clear evidence of the strong exciton–photon coupling). Here, we show that the strong light–matter coupling can occur beyond the microcavity device setup, i.e., between the ’free’ s(TE) photons and excitons. The s(TE) exciton–polariton is a polarization mode, which (contrary to the p(TM) mode) appears only as a coexistence of a photon and an exciton, i.e., it vanishes in the non-retarded limit (). We show that a thin fullerene C crystalline film (consisting of N C single layers) deposited on an AlO dielectric surface supports strong evanescent s(TE)-polarized exciton–polariton. The calculated Rabi splitting is more than meV for , with a tendency to increase with N, indicating a very strong photonic character of the exciton–polariton.

Triplet-triplet Annihilation Dynamics of Naphthalene.

Triplet‐triplet annihilation (TTA) is a spin‐allowed conversion of two triplet states into one singlet excited state, which provides an efficient route to generate a photon of higher frequency than the incident light. Multiple energy transfer steps between absorbing (sensitizer) and emitting (annihilator) molecular species are involved in the TTA based photon upconversion process. TTA compounds have recently been studied for solar energy applications, even though the maximum upconversion efficiency of 50 % is yet to be achieved. With the aid of quantum calculations and based on a few key requirements, several design principles have been established to develop the well‐functioning annihilators. However, a complete molecular level understanding of triplet fusion dynamics is still missing. In this work, we have employed multi‐reference electronic structure methods along with quantum dynamics to obtain a detailed and fundamental understanding of TTA mechanism in naphthalene. Our results suggest that the TTA process in naphthalene is mediated by conical intersections. In addition, we have explored the triplet fusion dynamics under the influence of strong light‐matter coupling and found an increase of the TTA based upconversion efficiency.

On the characteristic features of ionization in QED environments.

The ionization of molecular systems is important in many chemical processes, such as electron transfer and hot electron injection. Strong coupling between molecules and quantized fields (e.g., inside optical cavities) represents a new promising way to modify molecular properties in a non-invasive way. Recently, strong light-matter coupling has shown the potential to significantly improve the rates of hot electron driven processes, for instance, in water splitting. In this paper, we demonstrate that inside an optical cavity, the residual interaction between an outgoing free electron and the vacuum field is significant. We further show that since the quantized field is also interacting with the ionized molecule, the free electron and the molecular system are correlated. We develop a theoretical framework to account for the field induced correlation and show that the interaction between the free electron and the field, free electron-field interaction, has sizable effects on the ionization potential of typical organic molecules.

Spin Interference Effects in a Ring with Rashba Spin-Orbit Interaction Subject to Strong Light–Matter Coupling in Magnetic Field

Electron transport through a one-dimensional quantum ring, subjected to Rashba spin–orbit interaction and connected with two external leads, is studied in the presence of external fields. They include the optical radiation, produced by an off-resonant high-frequency electric field, and a perpendicular magnetic field. By means of the Floquet theory of periodically driven quantum systems the interference effects under these fields are described in detail. It is found analytically the specific conditions to reach the spin-filtering effect, caused by the interplay of the external fields and Rashba spin-orbit interaction.

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.

Frequency-Dependent Sternheimer Linear-Response Formalism for Strongly Coupled Light-Matter Systems.

The rapid progress in quantum-optical experiments, especially in the field of cavity quantum electrodynamics and nanoplasmonics, allows one to substantially modify and control chemical and physical properties of atoms, molecules, and solids by strongly coupling to the quantized field. Alongside such experimental advances has been the recent development of ab initio approaches such as quantum electrodynamical density-functional theory (QEDFT), which is capable of describing these strongly coupled systems from first principles. To investigate response properties of relatively large systems coupled to a wide range of photon modes, ab initio methods that scale well with system size become relevant. In light of this, we extend the linear-response Sternheimer approach within the framework of QEDFT to efficiently compute excited-state properties of strongly coupled light–matter systems. Using this method, we capture features of strong light–matter coupling both in the dispersion and absorption properties of a molecular system strongly coupled to the modes of a cavity. We exemplify the efficiency of the Sternheimer approach by coupling the matter system to the continuum of an electromagnetic field. We observe changes in the spectral features of the coupled system as Lorentzian line shapes turn into Fano resonances when the molecule interacts strongly with the continuum of modes. This work provides an alternative approach for computing efficiently excited-state properties of large molecular systems interacting with the quantized electromagnetic field.

Brightening of a dark monolayer semiconductor via strong light-matter coupling in a cavity

Engineering the properties of quantum materials via strong light-matter coupling is a compelling research direction with a multiplicity of modern applications. Those range from modifying charge transport in organic molecules, steering particle correlation and interactions, and even controlling chemical reactions. Here, we study the modification of the material properties via strong coupling and demonstrate an effective inversion of the excitonic band-ordering in a monolayer of WSe2 with spin-forbidden, optically dark ground state. In our experiments, we harness the strong light-matter coupling between cavity photon and the high energy, spin-allowed bright exciton, and thus creating two bright polaritonic modes in the optical bandgap with the lower polariton mode pushed below the WSe2 dark state. We demonstrate that in this regime the commonly observed luminescence quenching stemming from the fast relaxation to the dark ground state is prevented, which results in the brightening of this intrinsically dark material. We probe this effective brightening by temperature-dependent photoluminescence, and we find an excellent agreement with a theoretical model accounting for the inversion of the band ordering and phonon-assisted polariton relaxation.

Manipulating strong coupling between exciton and quasibound states in the continuum resonance

Strong coupling exhibits unique ability to preserve quantum sates between light and matter, which is essential for the development of quantum information technology. To explore the physical mechanism behind this phenomenon, we employ the tight-binding method for expanding the temporal coupled-mode theory, with the absorption spectrum formula of coupled system directly obtained in an analytical way. It reveals all the physical meaning of parameters defined in our theory, and shows how to tailor lineshapes of the coupled systems. Here, we set an example to manipulate the strong coupling in a hybrid structure composed of excitons in monolayer WS$_2$ and quasi-bound states in the continuum supported by the TiO$_2$ nanodisk metasurfaces. The simulated results show that a clear spectral splitting appeared in the absorption curve, which can be controlled by adjusting the asymmetric parameter of the nanodisk metasurfaces and well fitted through our theoretical predictions. Our work not only gives a more comprehensive understanding of such coupled systems, but also offers a promising strategy in controlling the strong light-matter coupling to meet diversified application requests.

Ultrastrong Coupling Leads to Slowed Cooling of Hot Excitons in Few-Layer Transition-Metal Dichalcogenides

The excited-state dynamics of few-layer molybdenum disulfide (FL-MoS2) are studied in conditions of strong light–matter coupling to plasmon polaritons. Hot carrier extraction in these systems has been proposed due to the observation of slow cooling of the high-energy C exciton relative to the bandgap A exciton. Here, we show that in conditions of ultrastrong coupling to plasmon polaritons, the lifetimes of the two slowest C exciton decay processes are extended by factors of 1.5 and 5.8 in FL-MoS2. We hypothesize that strong coupling delocalization suppresses multiple decay mechanisms throughout the visible spectrum in MoS2 such as defect scattering, intervalley scattering of band-nested excitations to the Κ-valley band edges, and exciton–exciton annihilation. We also find that decay from the upper to the lower hybrid mode is not ultrafast as seen in organic systems but in fact introduces an additional delay of ∼20 ps. Our observations show that strong coupling can be used to extend the lifetimes of hot excitons in FL-MoS2 and potentially in other two-dimensional transition-metal dichalcogenides, with potential for above-bandgap photophysics and photochemistry applications such as hot carrier extraction, which could lead to more efficient solar energy conversion.

Microcavity Exciton‐Polariton Quantum Spin Fluids

AbstractMicrocavity exciton‐polaritons are attractive quantum quasi‐particles resulting from strong light–matter coupling in a quantum‐well‐cavity structure. They have become one of the most stimulating solid‐state material platforms to explore beautiful collective quantum phenomena originating from macroscopic coherence in condensation and superfluidity, Berezinskii–Kosterlitz–Thouless transition, and various topological excitations in the form of solitons, vortices, and skyrmions. They can also provide opportunities for the development of pioneering photonic devices by exploiting bistability and parametric scatterings due to strong nonlinearity that possess remarkable performance advantages of power‐efficient operation, ultrafast response time, and scalable planar geometries. This story becomes profound and fascinating when the spins of excitons are taken into account, that can be directly accessed through light polarization states. The purpose of this review is to give central principles of microcavity exciton‐polariton spins and their anisotropic interactions, which can couple with the effective magnetic fields from mode‐splitting of microcavity photons and spin‐dependent relaxation processes of quantum‐well excitons. Furthermore, notable theoretical and experimental research activities are summarized to reveal extraordinary quantum phenomena of spin‐resolved topological states and exotic spin textures and to devise novel spin‐based photonic devices based on microcavity exciton‐polaritons.

Optomagnonics in Dispersive Media: Magnon-Photon Coupling Enhancement at the Epsilon-near-Zero Frequency.

Reaching strong light-matter coupling in solid-state systems has long been pursued for the implementation of scalable quantum devices. Here, we put forward a system based on a magnetized epsilon-near-zero (ENZ) medium, and we show that strong coupling between magnetic excitations (magnons) and light can be achieved close to the ENZ frequency due to a drastic enhancement of the magneto-optical response. We adopt a phenomenological approach to quantize the electromagnetic field inside a dispersive magnetic medium in order to obtain the frequency-dependent coupling between magnons and photons. We predict that, in the epsilon-near-zero regime, the single-magnon single-photon coupling can be comparable to the magnon frequency for a small magnetic volume and perfect mode overlap. For state-of-the-art illustrative values, this would correspond to achieving the single-magnon strong coupling regime, where the coupling rate is larger than all the decay rates. Finally, we show that the nonlinear energy spectrum intrinsic to this coupling regime can be probed via the characteristic multiple magnon sidebands in the photon power spectrum.

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.

Effective theory of lattice electrons strongly coupled to quantum electromagnetic fields

Recent experiments have revealed the tantalizing possibility of fabricating lattice electronic systems strongly coupled to quantum fluctuations of electromagnetic fields, e.g., by means of geometry confinement from a cavity or artificial gauge fields in quantum simulators. In this work, we develop a high-frequency expansion to construct the effective models for lattice electrons strongly coupled to a continuum of off-resonant photon modes with arbitrary dispersion. The theory is nonperturbative in the light-matter coupling strength, and is therefore particularly suitable for the ultrastrong light-matter coupling regime. Using the effective models, we demonstrate how the dispersion and topology of the electronic energy bands can be tuned by the cavity. In particular, quasi-one-dimensional physics can emerge in a two-dimensional square lattice due to a spatially anisotropic band renormalization, and a topologically nontrivial anomalous quantum Hall state can be induced in a honeycomb lattice when the cavity setup breaks time-reversal symmetry. We also demonstrate that the photon-mediated interaction induces an unconventional superconducting paired phase distinct from the pair-density-wave state discussed in models with truncated light-matter coupling. Finally, we study a realistic setup of a Fabry-P\'{e}rot cavity. Our work provides a systematic framework to explore the emergent phenomena due to strong light-matter coupling and points out new directions of engineering orders and topological states in solids.

Direct Polariton-To-Electron Tunneling in Quantum Cascade Detectors Operating in the Strong Light-Matter Coupling Regime

Modern optoelectronic devices rely on cavity electrodynamics concepts for improved performances, embedding the active medium in an optical cavity to enhance the light-matter coupling. This coupling rate is usually small compared to the electronic and photon energies. Despite several demonstrations, devices operating with much larger light-matter coupling strength, in the so-called strong light-matter coupling regime, are yet to be demonstrated as viable, practical candidates. One of the main technological obstacles that hamper their dissemination is the comprehension of the carrier current extraction and injection from and into strongly coupled light-matter states. Here, we study this fundamental phenomenon in midinfrared quantum cascade detectors (QCDs) operating in the moderate to strong light-matter coupling regime. They operate around $\ensuremath{\lambda}=10\phantom{\rule{0.2em}{0ex}}\ensuremath{\mu}\mathrm{m}$ with a minimum Rabi splitting of 9.3 meV. A simple model based on the usual description of transport in QCDs does not reproduce the polaritonic features in the photocurrent spectra. On the contrary, a more refined approach, based on the semiclassical coupled modes theory, is capable of reproducing both optical and electrical spectra with excellent agreement. By correlating absorption and photoresponse with the simulations, we demonstrate that---in this system---resonant tunneling from the polaritonic states appears to be the predominant extraction mechanism. The dark intersubband states do not have a significant role in the process, contrary to what happens in electrically injected polaritonic emitters.

Optical Cavity Manipulation and Nonlinear UV Molecular Spectroscopy of Conical Intersections in Pyrazine.

Optical cavities provide a versatile platform for manipulating the excited-state dynamics of molecules via strong light-matter coupling. We employ optical absorption and two-multidimensional electronic spectroscopy simulations to investigate the effect of optical cavity coupling in the nonadiabatic dynamics of photoexcited pyrazine. We observe the emergence of a novel polaritonic conical intersection (PCI) between the electronic dark state and photonic surfaces as the cavity frequency is tuned. The PCI could significantly change the nonadiabatic dynamics of pyrazine by doubling the decay rate constant of the S2 state population. Moreover, the absorption spectrum and excited-state dynamics could be systematically manipulated by tuning the strong light-matter interaction, e.g., the cavity frequency and cavity coupling strength. We propose that a tunable optical cavity-molecule system may provide promising approaches for manipulating the photophysical properties of molecules.

Ab Initio Linear-Response Approach to Vibro-Polaritons in the Cavity Born-Oppenheimer Approximation.

Recent years have seen significant developments in the study of strong light–matter coupling including the control of chemical reactions by altering the vibrational normal modes of molecules. In the vibrational strong coupling regime, the normal modes of the system become hybrid modes which mix nuclear, electronic, and photonic degrees of freedom. First-principles methods capable of treating light and matter degrees of freedom on the same level of theory are an important tool in understanding such systems. In this work, we develop and apply a generalized force constant matrix approach to the study of mixed vibration-photon (vibro-polariton) states of molecules based on the cavity Born–Oppenheimer approximation and quantum-electrodynamical density-functional theory. With this method, vibro-polariton modes and infrared spectra can be computed via linear-response techniques analogous to those widely used for conventional vibrations and phonons. We also develop an accurate model that highlights the consistent treatment of cavity-coupled electrons in the vibrational strong coupling regime. These electronic effects appear as new terms previously disregarded by simpler models. This effective model also allows for an accurate extrapolation of single and two molecule calculations to the collective strong coupling limit of hundreds of molecules. We benchmark these approaches for single and many CO2 molecules coupled to a single photon mode and the iron pentacarbonyl Fe(CO)5 molecule coupled to a few photon modes. Our results are the first ab initio results for collective vibrational strong coupling effects. This framework for efficient computations of vibro-polaritons paves the way to a systematic description and improved understanding of the behavior of chemical systems in vibrational strong coupling.

Optimizing molecular light absorption in the strong coupling regime for solar energy harvesting

The strong coupling of optical absorbers (e.g., molecules or semiconductors) to confined photonic modes fundamentally alters the physical properties of the coupled system via the formation of hybrid light-matter states. One potential application of strong light-matter coupling relies on exploiting it to localize light-induced charge excitation processes to small volumes of material. Applications that would benefit from this localization include thin-film photovoltaics, photodetection, photocatalysis, and others, where the overall performance depends on the ability of a material to amplify light absorption (i.e., the formation of electron-hole pairs) within specific locations in space. This contribution investigates how strong light-matter coupling affects light absorption rates in molecular absorbers coupled to photonic nanostructures. Our results show that the molecular light absorption efficiencies are highest in configurations where the strongly coupled molecules interact directly with the incoming photon flux. We also identify a nonlinear dependence in the molecular absorption as a function of concentration, unique to the strongly coupled systems. Based on these results, we propose design principles for engineering nanostructured systems that allow for high efficiencies of charge carrier localization into strongly coupled absorbers.