Strong Light-matter Coupling Research Articles

Reversible Switching of Strong Light-Matter Coupling Using Spin-Crossover Molecular Materials.

The formation of hybrid light-matter states through the resonant interaction of confined electromagnetic fields with matter excitations has emerged as a fascinating tool for controlling quantum-mechanical states and then manipulating the functionalities and chemical reactivity landscape of molecular materials. Here we report the first observation of switchable strong light-matter coupling involving bistable spin-crossover molecules. Spectroscopic measurements, supported by transfer-matrix and coupled-oscillator simulations, reveal Rabi splitting values of up to 550 meV, which at 15% of the molecular excitation energy enter the regime of ultrastrong coupling. We find that the thermally induced switching of molecules between their low-spin and high-spin states allows fine control of the light-matter hybridization strength, offering the appealing possibility of reversible switching between the ultrastrong- and weak-coupling regimes within a single photonic structure. Through this work, we show that spin-crossover molecular compounds constitute a promising class of active nanomaterials in the burgeoning context of tunable polaritonic devices and polaritonic chemistry.

Developing Solution-Processed Distributed Bragg Reflectors for Microcavity Polariton Applications.

Improving the performance of organic optoelectronics has been under vigorous research for decades. Recently, polaritonics has been introduced as a technology that has the potential to improve the optical, electrical, and chemical properties of materials and devices. However, polaritons have been mainly studied in optical microcavities that are made by vacuum deposition processes, which are costly, unavailable to many, and incompatible with printed optoelectronics methods. Efforts toward the fabrication of polariton microcavities with solution-processed techniques have been utterly absent. Herein, we demonstrate for the first time strong light-matter coupling and polariton photoluminescence in an organic microcavity consisting of an aluminum mirror and a distributed Bragg reflector (DBR) made by sequential dip coating of titanium hydroxide/poly(vinyl alcohol) (TiOH/PVA) and Nafion films. To fabricate and develop the solution-processed DBRs and microcavities, we automatized a dip-coating device that allowed us to produce sub-100 nm films consistently over many dip-coating cycles. Owning to the solution-based nature of our DBRs, our results pave the way to the realization of polariton optoelectronic devices beyond physical deposition methods.

Spin-selective strong light–matter coupling in a 2D hole gas-microcavity system

Spin-selective strong light–matter coupling in a 2D hole gas-microcavity system

Simple and Versatile Platforms for Manipulating Light with Matter: Strong Light-Matter Coupling in Fully Solution-Processed Optical Microcavities.

Planar microcavities with strong light-matter coupling, monolithically processed fully from solution, consisting of two polymer-based distributed Bragg reflectors (DBRs) comprising alternating layers of a high-refractive-index titanium oxide hydrate/poly(vinyl alcohol) hybrid material and a low-refractive-index fluorinated polymer are presented. The DBRs enclose a perylene diimide derivative (b-PDI-1) film positioned at the antinode of the optical mode. Strong light-matter coupling is achieved in these structures at the target excitation of the b-PDI-1. Indeed, the energy-dispersion relation (energy vs in-plane wavevector or output angle) in reflectance and the group delay of transmitted light in the microcavities show a clear anti-crossing-an energy gap between two distinct exciton-polariton dispersion branches. The agreement between classical electrodynamic simulations of the microcavity response and the experimental data demonstrates that the entire microcavity stack can be controllably produced as designed. Promisingly, the refractive index of the inorganic/organic hybrid layers used in the microcavity DBRs can be precisely manipulated between values of 1.50 to 2.10. Hence, microcavities with a wide spectral range of optical modes might be designed and produced with straightforward coating methodologies, enabling fine-tuning of the energy and lifetime of the microcavities' optical modes to harness strong light-matter coupling in a wide variety of solution processable active materials.

Interspecies exciton interactions lead to enhanced nonlinearity of dipolar excitons and polaritons in MoS2 homobilayers

Nonlinear interactions between excitons strongly coupled to light are key for accessing quantum many-body phenomena in polariton systems. Atomically-thin two-dimensional semiconductors provide an attractive platform for strong light-matter coupling owing to many controllable excitonic degrees of freedom. Among these, the recently emerged exciton hybridization opens access to unexplored excitonic species, with a promise of enhanced interactions. Here, we employ hybridized interlayer excitons (hIX) in bilayer MoS2 to achieve highly nonlinear excitonic and polaritonic effects. Such interlayer excitons possess an out-of-plane electric dipole as well as an unusually large oscillator strength allowing observation of dipolar polaritons (dipolaritons) in bilayers in optical microcavities. Compared to excitons and polaritons in MoS2 monolayers, both hIX and dipolaritons exhibit ≈ 8 times higher nonlinearity, which is further strongly enhanced when hIX and intralayer excitons, sharing the same valence band, are excited simultaneously. This provides access to an unusual nonlinear regime which we describe theoretically as a mixed effect of Pauli exclusion and exciton-exciton interactions enabled through charge tunnelling. The presented insight into many-body interactions provides new tools for accessing few-polariton quantum correlations.

Intrinsic strong light-matter coupling with self-hybridized bound states in the continuum in van der Waals metasurfaces.

Photonic bound states in the continuum (BICs) provide a standout platform for strong light-matter coupling with transition metal dichalcogenides (TMDCs) but have so far mostly been implemented as traditional all-dielectric metasurfaces with adjacent TMDC layers, incurring limitations related to strain, mode overlap and material integration. Here, we demonstrate intrinsic strong coupling in BIC-driven metasurfaces composed of nanostructured bulk tungsten disulfide (WS2) and exhibiting resonances with sharp, tailored linewidths and selective enhancement of light-matter interactions. Tuning of the BIC resonances across the exciton resonance in bulk WS2 is achieved by varying the metasurface unit cells, enabling strong coupling with an anticrossing pattern and a Rabi splitting of 116 meV. Crucially, the coupling strength itself can be controlled and is shown to be independent of material-intrinsic losses. Our self-hybridized metasurface platform can readily incorporate other TMDCs or excitonic materials to deliver fundamental insights and practical device concepts for polaritonic applications.

Toward Molecular Chiral Polaritons

Coupling between light and material excitations underlies a wide range of optical phenomena. Polaritons are eigenstates of a coupled system with a hybridized wave function. Owing to their hybrid composition, polaritons exhibit at the same time properties typical for photonic and electronic excitations, thus offering new ways for controlling electronic transport and even chemical kinetics. While most theoretical and experimental efforts have been focused on polaritons with electric-dipole coupling between light and matter, in chiral quantum emitters, electronic transitions are characterized by simultaneously nonzero electric and magnetic dipole moments. Thus, it is natural to wonder what kinds of novel effects chirality may enable in the realm of strong light–matter coupling. Right now, this field located at the intersection of nanophotonics, quantum optics, and chemistry is in its infancy. In this Perspective, we offer our view toward chiral polaritons. We review basic physical concepts underlying chirality of matter and electromagnetic field, discuss the main theoretical and experimental challenges that need to be solved, and consider novel effects that could be enabled by strong coupling between chiral light and matter.

Theoretical Analysis of Exciton Wave Packet Dynamics in Polaritonic Wires.

We present a comprehensive study of the exciton wave packet evolution in disordered lossless polaritonic wires. Our simulations reveal signatures of ballistic, diffusive, and subdiffusive exciton dynamics under strong light-matter coupling and identify the typical time scales associated with the transitions between these qualitatively distinct transport phenomena. We determine optimal truncations of the matter and radiation subsystems required for generating reliable time-dependent data from computational simulations at an affordable cost. The time evolution of the photonic part of the wave function reveals that many cavity modes contribute to the dynamics in a nontrivial fashion. Hence, a sizable number of photon modes is needed to describe exciton propagation with a reasonable accuracy. We find and discuss an intriguingly common lack of dominance of the photon mode on resonance with matter in both the presence and absence of disorder. We discuss the implications of our investigations for the development of theoretical models and analysis of experiments where coherent intermolecular energy transport and static disorder play an important role.

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.

Long-Range Energy Transfer in Strongly Coupled Donor-Acceptor Phototransistors.

Strong light-matter coupling offers a way to tailor the optoelectronic properties of materials. Energy transfer between strongly coupled donor-acceptor pairs shows remarkable efficiency beyond the Förster distance via coupling through a confined photon. This long-range energy transfer is facilitated through the collective nature of polaritonic states. Here, the cooperative, strong coupling of a donor (MoS2 monolayer) and an acceptor (BRK) generates mixed polaritonic states. The photocurrent spectrum of the MoS2 monolayer is measured in a field effect transistor while coupling the two oscillators to the confined cavity mode. The strongly coupled system shows efficient energy transfer, which is observed through the photoresponsivity even the donor and acceptor are physically separated by 500 Å. These studies are further correlated with the Hopfield coefficients and the overlap integral of the lower polaritonic and uncoupled/dark states. Cavity detuning and distance-dependent studies support the above evidence. These observations open new avenues for using long-range interaction of polaritonic states in optoelectronic devices.

Polariton Localization and Dispersion Properties of Disordered Quantum Emitters in Multimode Microcavities.

Experiments have demonstrated that the strong light-matter coupling in polaritonic microcavities significantly enhances transport. Motivated by these experiments, we have solved the disordered multimode Tavis-Cummings model in the thermodynamic limit and used this solution to analyze its dispersion and localization properties. The solution implies that wave-vector-resolved spectroscopic quantities can be described by single-mode models, but spatially resolved quantities require the multimode solution. Nondiagonal elements of the Green's function decay exponentially with distance, which defines the coherence length. The coherent length is strongly correlated with the photon weight and exhibits inverse scaling with respect to the Rabi frequency and an unusual dependence on disorder. For energies away from the average molecular energy E_{M} and above the confinement energy E_{C}, the coherence length rapidly diverges such that it exceeds the photon resonance wavelength λ_{0}. The rapid divergence allows us to differentiate the localized and delocalized regimes and identify the transition from diffusive to ballistic transport.

Two-dimensional coherent spectroscopy of trion-polaritons and exciton-polaritons in atomically thin transition metal dichalcogenides

We present a microscopic many-body calculation of the nonlinear two-dimensional coherent spectroscopy (2DCS) of trion-polaritons and exciton-polaritons in charge-tunable transition-metal-dichalcogenides monolayers placed in an optical microcavity. The charge tunability leads to an electron gas with nonzero density that brings brightness to the trion — a polaron quasiparticle formed by an exciton with a nonzero residue bounded to the electron gas. As a result, a trion-polariton is created under strong light-matter coupling, as observed in the recent experiment by Sidler et al. [Nat. Phys. 13, 255 (2017)]. We analyze in detail the structure of trion-polaritons, by solving an extended Chevy ansatz for the trion quasiparticle wave-function. We confirm that the effective light-matter coupling for trion-polaritons is determined by the residue of the trion quasiparticle. The solution of the full many-body polaron states within Chevy ansatz enables us to microscopically calculate the nonlinear 2DCS spectrum of both trion-polaritons and exciton-polaritons. We predict the existence of three kinds of off-diagonal cross-peaks in the 2DCS spectrum, as an indication of the coherence among the different branches of trion-polaritons and exciton-polaritons. Due to the sensitivity of 2DCS spectrum to quasiparticle interactions, our work provides a good starting point to explore the strong nonlinearity exhibited by trion-polaritons in some recent exciton-polariton experiments.

Enhanced Two-Dimensional Exciton Propagation via Strong Light–Matter Coupling with Surface Lattice Plasmons

Exciton–polaritons─hybrid exciton–photon quasi-particles─have enabled exciting long-range coherent transport by taking advantage of the properties of their photonic component. However, most experimental demonstrations of strong coupling have been based on semiconductor Fabry–Pérot microcavities. Here, we report an open and versatile exciton–polariton platform by integrating two-dimensional lead halide perovskites with plasmonic nanoparticle arrays, which support hybridization between excitons and surface lattice resonances in the strong coupling regime. Benefitting from the open architecture, we directly visualized polariton-enhanced exciton transport via angle-dependent transient absorption microscopy measurements. The observed transport enhancement extends into the picosecond timescale, leading to more than 1 order of magnitude improvement of exciton migration, from ∼10 nm to 100s of nanometers. We proposed a polariton-mediated exciton transport model and obtained an average polariton velocity of ∼1 × 106 m/s for states with an ∼40% photonic fraction. These results demonstrate plasmonic particle arrays as a versatile and adaptable cavity to enhance exciton transport.

Probing correlated states with plasmons.

Understanding the nature of strongly correlated states in flat-band materials (such as moiré heterostructures) is at the forefront of both experimental and theoretical pursuits. While magnetotransport, scanning probe, and optical techniques are often very successful in investigating the properties of the underlying order, the exact nature of the ground state often remains unknown. Here, we propose to leverage strong light-matter coupling present in the flat-band systems to gain insight through dynamical dielectric response into the structure of the many-body ground state. We argue that because of the enlargement of the effective lattice of the system arising from correlations, conventional long-range plasmon becomes "folded" to yield a multiband plasmon spectrum. We detail several mechanisms through which the structure of the plasmon spectrum and that of the dynamical dielectric response is susceptible to the underlying order, revealing valued insights such as the interaction-driven band gaps, spin-structure, and the order periodicity.

Comparing semiclassical mean-field and 1-exciton approximations in evaluating optical response under strong light-matter coupling conditions.

The rigorous quantum mechanical description of the collective interaction of many molecules with the radiation field is usually considered numerically intractable, and approximation schemes must be employed. Standard spectroscopy usually contains some levels of perturbation theory, but under strong coupling conditions, other approximations are used. A common approximation is the 1-exciton model in which processes involving weak excitations are described using a basis comprising the ground state and singly excited states of the molecule cavity-mode system. In another frequently used approximation in numerical investigations, the electromagnetic field is described classically, and the quantum molecular subsystem is treated in the mean-field Hartree approximation with its wavefunction assumed to be a product of single molecules' wavefunctions. The former disregards states that take long time to populate and is, therefore, essentially a short time approximation. The latter is not limited in this way, but by its nature, disregards some intermolecular and molecule-field correlations. In this work, we directly compare results obtained from these approximations when applied to several prototype problems involving the optical response of molecules-in-optical cavities systems. In particular, we show that our recent model investigation [J. Chem. Phys. 157, 114108 (2022)] of the interplay between the electronic strong coupling and molecular nuclear dynamics using the truncated 1-exciton approximation agrees very well with the semiclassical mean-field calculation.

Control and Enhancement of Single-Molecule Electroluminescence through Strong Light–Matter Coupling

The energetic positions of molecular electronic states at molecule/electrode interfaces are crucial factors for determining the transport and optoelectronic properties of molecular junctions. Strong light-matter coupling offers a potential for manipulating these factors, enabling a boost in the efficiency and versatility of these junctions. Here, we investigate electroluminescence from single-molecule junctions in which the molecule is strongly coupled with the vacuum electromagnetic field in a plasmonic nanocavity. We demonstrate an improvement in the electroluminescence efficiency by employing the strong light-matter coupling in conjunction with the characteristic feature of single-molecule junctions to selectively control the formation of the lowest-energy excited state. The mechanism of efficiency improvement is discussed based on the energetic position and composition of the formed polaritonic states. Our findings indicate the possibility to manipulate optoelectronic conversion in molecular junctions by strong light-matter coupling and contribute to providing design principles for developing efficient molecular optoelectronic devices.

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.

Highly efficient polaritonic light-emitting diodes with angle-independent narrowband emission

Angle-independent narrowband emission is required for many optoelectronic devices, ranging from high-definition displays to sensors. However, emerging materials for electroluminescent devices, such as organics and perovskites, show spectrally broad emission due to intrinsic disorder. Coupling this emission to an optical resonance reduces the linewidth, but at the cost of inheriting the severe angular dispersion of the resonator. Strongly coupling a dispersionless exciton state to a narrowband optical microcavity could overcome this issue; however, electrically pumped emission from the resulting polaritons is typically hampered by poor efficiencies. Here we present a universal concept for polariton-based emission from organic light-emitting diodes by introducing an assistant strong coupling layer, thereby avoiding quenching-induced efficiency losses. We realize red- and green-emitting, narrowband (full-width at half-maximum of less than 20 nm) and spectrally tunable polaritonic organic light-emitting diodes with up to 10% external quantum efficiency and high luminance (>20,000 cd m−2 at 5 V). By optimizing cavity detuning and coupling strength, we achieve emission with ultralow dispersion (<10 nm spectral shift at 60° tilt). These results may have wide-reaching implications for on-demand polariton emission and demonstrate the practical relevance of strong light–matter coupling for next-generation optoelectronics, particularly display technology.

Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis.

Strong light-matter coupling offers a unique way to control chemical reactions at the molecular level. Here, we compare the solvent effect on an ester solvolysis process under cooperative vibrational strong coupling (VSC). Three reactants, para-nitrophenylacetate, 3-methyl-para-nitrophenylbenzoate, and bis-(2, 4-dinitrophenyl) oxalate are chosen to study the effect of VSC on the solvolysis reaction rates. Two solvents, ethyl acetate and cyclopentanone, are also considered to compare the cavity catalysis by coupling the C=O stretching band of the reactant and the solvent molecules to a Fabry-Perot cavity mode. Interestingly, both solvents enhance the chemical reaction rate of para-nitrophenylacetate and 3-methyl-para-nitrophenylbenzoate under cooperative VSC conditions. However, the resonance effect is observed at different temperatures for different solvents, which is further confirmed by thermodynamic studies. Bis-(2, 4-dinitrophenyl) oxalate doesn't respond to VSC in either of the solvent systems due to poor overlap of reactant and solvent C=O vibrational bands. Cavity detuning and other control experiments suggest that cooperative VSC of the solvent plays a crucial role in modifying the activation free-energy of the reaction. These findings, along with other observations, cement the concept of polaritonic chemistry.

Perturbation theoretical approaches to strong light-matter coupling in ground and excited electronic states for the description of molecular polaritons.

Quantum chemical methods for the description of molecular polaritonic states in the strong coupling regime based on the Pauli-Fierz Hamiltonian are introduced. Based on a quantum electrodynamic Hartree-Fock (QED-HF) reference, a QED Møller-Plesset perturbation theory of second order for the electronic ground state and a second order quantum electrodynamic algebraic diagrammatic construction scheme for the polarization propagator [QED-ADC(2)] for excited electronic states have been derived, implemented, and tested for polaritons in hydrogen fluoride. Analogous approaches based on a standard non-polaritonic HF reference are also presented and thoroughly compared, both algebraically and numerically, to those based on the QED-HF reference. Furthermore, a promising route to approximate QED-ADC methods based on a unitary transformation of the algebraic expression into a restricted state space is outlined showing excellent agreement in second order with QED-ADC(2). All presented novel methods are compared to and tested against other existing abinitio approaches, mostly QED coupled cluster theory, including single and double excitations, and show qualitative agreement at a reduced computational effort.