Hybrid Light-matter Research Articles

Effects of Self-Hybridized Exciton-Polaritons on TMDC Photovoltaics.

Hybrid light-matter states called exciton-polaritons have been explored to improve excitonic photovoltaic (PV) and photodiode efficiency, but the use of closed cavity structures results in efficiency gains over a narrow band, with losses in the short circuit current density under solar illumination. In WX2 (X = S, Se), the simultaneous large optical constants and strong exciton resonance can result in self-hybridized exciton-polaritons (SHEPs) emerging from the strong coupling of excitons and optical cavity modes formed by WX2. We perform thickness dependent device characterization of WS2 and WSe2 PVs to show that self-hybridized strong coupling enhances device efficiency on resonance while still enabling broadband absorption, resulting in improved short circuit current density under solar illumination. Ultimately, we leverage strong coupling to achieve external quantum efficiencies as high as 70% and record power conversion efficiencies approaching 7%. This result indicates the utility of SHEPs for light-energy harvesting applications.

Quantum Dynamics Simulations of Exciton Polariton Transport.

Recent experiments have shown that exciton transport can be significantly enhanced through hybridization with confined photonic modes in a cavity. The light-matter hybridization generates exciton-polariton (EP) bands, whose group velocity is significantly larger than the excitons. Dissipative mechanisms that affect the constituent states of EPs, such as exciton-phonon coupling and cavity loss, have been observed to reduce the group velocities in experiments. To elucidate the impacts of these dissipative mechanisms on polariton transport, we developed an efficient quantum dynamics approach that allows us to directly simulate polariton transport under the collective coupling regime and beyond long-wavelength approximation. Our numerical results suggest a renormalization of the group velocities with stronger exciton-phonon coupling strengths and a smaller Q-factor. We observe the transition from ballistic to diffusive propagation as well as the quality-factor-dependent behavior of the transient mean square displacement, agreeing well with the recent experimental measurements.

Analytical derivative approaches for vibro-polaritonic structures and properties. I. Formalism and implementation.

Vibro-polaritons are hybrid light-matter states that arise from the strong coupling between the molecular vibrational transitions and the photons in an optical cavity. Developing theoretical and computational methods to describe and predict the unique properties of vibro-polaritons is of great significance for guiding the design of new materials and experiments. Here, we present the abinitio cavity Born-Oppenheimer density functional theory (CBO-DFT) and formulate the analytic energy gradient and Hessian as well as the nuclear and photonic derivatives of dipole and polarizability within the framework of CBO-DFT to efficiently calculate the harmonic vibrational frequencies, infrared absorption, and Raman scattering spectra of vibro-polaritons as well as to explore the critical points on the cavity potential energy surface. The implementation of analytic derivatives into the electronic structure package is validated by a comparison with the finite-difference method and with other reported computational results. By adopting appropriate exchange-correlation functionals, CBO-DFT can better describe the structure and properties of molecules in the cavity than CBO-Hartree-Fock method. It is expected that CBO-DFT is a useful tool for studying the polaritonic structures and properties.

Disentangling collective coupling in vibrational polaritons with double quantum coherence spectroscopy.

Vibrational polaritons are formed by strong coupling of molecular vibrations and photon modes in an optical cavity. Experiments have demonstrated that vibrational strong coupling can change molecular properties and even affect chemical reactivity. However, the interactions in a molecular ensemble are complex, and the exact mechanisms that lead to modifications are not fully understood yet. We simulate two-dimensional infrared spectra of molecular vibrational polaritons based on the double quantum coherence technique to gain further insight into the complex many-body structure of these hybrid light-matter states. Double quantum coherence uniquely resolves the excitation of hybrid light-matter polaritons and allows one to directly probe the anharmonicities of the resulting states. By combining the cavity Born-Oppenheimer Hartree-Fock ansatz with a full quantum dynamics simulation of the corresponding eigenstates, we go beyond simplified model systems. This allows us to study the influence of self-polarization and the response of the electronic structure to the cavity interaction on the spectral features even beyond the single-molecule case.

Quantum origin of anomalous Floquet phases in cavity-QED materials

Anomalous Floquet topological phases are unique to periodically driven systems, lacking a static analog. Inspired by Floquet Engineering with classical electromagnetic radiation, Quantum Floquet Engineering has emerged as a promising tool to tailor the properties of quantum materials using quantum light. While the latter recovers the physics of Floquet materials in its semi-classical limit, the mapping between these two scenarios remains mysterious in many aspects. In this work, we discuss the emergence of quantum anomalous topological phases in cavity-QED materials, linking the topological phase transitions in the electron-photon spectrum with those in the 0- and π-gaps of Floquet quasienergies. Our results establish the microscopic origin of an emergent discrete time-translation symmetry in the matter sector, and link isolated c-QED materials with periodically driven ones. Finally, we discuss the bulk-edge correspondence in terms of hybrid light-matter topological invariants.

Plasmon-Exciton Strong Coupling in Single-Molecule Junction Electroluminescence.

Single molecules bridging two metallic electrodes can emit light through electroluminescence when subjected to a bias voltage. Typically, light emission in such devices results from transitions between molecular states, although in the presence of light-matter coupling, the emission can result from a transition between hybrid light-matter states. Here, we create single metal-molecule-metal junctions and simultaneously collect conductance and electroluminescence data using a scanning tunneling microscope (STM) equipped with a custom spectrometer. Through experimental analysis and electronic structure calculations, we provide evidence for a molecule-electrode interfacial exciton coupled to a junction cavity plasmon. Importantly, we find that close to resonant transport conditions, the molecular junction functions as a single emitter that is strongly coupled to the junction cavity mode, leading to characteristic Rabi splitting of the emission spectrum and providing the first example of an electroluminescence-driven single-molecule system in the regime of strong light-matter coupling.

Cavity induced modulation of intramolecular vibrational energy flow pathways.

Recent experiments in polariton chemistry indicate that reaction rates can be significantly enhanced or suppressed inside an optical cavity. One possible explanation for the rate modulation involves the cavity mode altering the intramolecular vibrational energy redistribution (IVR) pathways by coupling to specific molecular vibrations in the vibrational strong coupling (VSC) regime. However, the mechanism for such a cavity-mediated modulation of IVR is yet to be understood. In a recent study, Ahn et al. [Science 380, 1165 (2023)] observed that the rate of alcoholysis of phenyl isocyanate (PHI) is considerably suppressed when the cavity mode is tuned to be resonant with the isocyanate (NCO) stretching mode of PHI. Here, we analyze the quantum and classical IVR dynamics of a model effective Hamiltonian for PHI involving the high-frequency NCO-stretch mode and two of the key low-frequency phenyl ring modes. We compute various indicators of the extent of IVR in the cavity-molecule system and show that tuning the cavity frequency to the NCO-stretching mode strongly perturbs the cavity-free IVR pathways. Subsequent IVR dynamics involving the cavity and the molecular anharmonic resonances lead to efficient scrambling of an initial NCO-stretching overtone state over the molecular quantum number space. We also show that the hybrid light-matter states of the effective Hamiltonian undergo a localization-delocalization transition in the VSC regime.

Long-Range Ballistic Propagation of 80% Excitonic Fraction Polaritons in a Perovskite Metasurface at Room Temperature.

Exciton-polaritons, hybrid light-matter excitations arising from the strong coupling between excitons in semiconductors and photons in photonic nanostructures, are crucial for exploring the physics of quantum fluids of light and developing all-optical devices. Achieving room temperature propagation of polaritons with a large excitonic fraction is challenging but vital, e.g., for nonlinear light transport. We report on room temperature propagation of exciton-polaritons in a metasurface made from a subwavelength lattice of perovskite pillars. The large Rabi splitting, much greater than the optical phonon energy, decouples the lower polariton band from the phonon bath of the perovskite. These cooled polaritons, in combination with the high group velocity achieved through the metasurface design, enable long-range propagation, exceeding hundreds of micrometers even with an 80% excitonic component. Furthermore, the design of the metasurface introduces an original mechanism for unidirectional propagation through polarization control, suggesting a new avenue for the development of advanced polaritonic devices.

Room temperature polariton spin switches based on Van der Waals superlattices

Transition-metal dichalcogenide monolayers possess large exciton binding energy and a robust valley degree of freedom, making them a viable platform for the development of spintronic devices capable of operating at room temperature. The development of such monolayer TMD-based spintronic devices requires strong spin-dependent interactions and effective spin transport. This can be achieved by employing exciton-polaritons. These hybrid light-matter states arising from the strong coupling of excitons and photons allow high-speed in-plane propagation and strong nonlinear interactions. Here, we demonstrate the operation of all-optical polariton spin switches by incorporating a WS2 superlattice into a planar microcavity. We demonstrate spin-anisotropic polariton nonlinear interactions in a WS2 superlattice at room temperature. As a proof-of-concept, we utilize these spin-dependent interactions to implement different spin switch geometries at ambient conditions, which show intrinsic sub-picosecond switching time and small footprint. Our findings offer new perspectives on manipulations of the polarization state in polaritonic systems and highlight the potential of atomically thin semiconductors for the development of next generation information processing devices.

Making molecules in cavity.

Free molecules undergo processes with photons; in particular, they can undergo photoionization and photodissociation, which are relevant processes in nature and laboratory. Recently, it has been shown that in a cavity, the reverse process of photoionization, namely, electron capture becomes highly probable. The underlying mechanism is the formation of a hybrid resonance state. In this work, we demonstrate that the idea of enhanced reverse processes is more general. We discuss the case of the reverse process of photodissociation, namely, making a molecule out of separate atoms in a cavity. For bound electronic states, the interaction of atoms and molecules with quantum light as realized in cavities is known to give rise to the formation of hybrid light-matter states (usually called polaritons). In the scenarios discussed here, the hybrid light-matter states are resonance (metastable) states, which decay into the continuum of either electrons or of the fragments of a molecule. Resonances can substantially enhance the outcome of processes. In addition to the new resonant mechanism of molecule formation, the impact of the hybrid resonances on the scattering cross section of the atoms can be dramatic.

Hybrid light-matter states in topological superconductors coupled to cavity photons

Hybrid light-matter states in topological superconductors coupled to cavity photons

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.

Photophysical properties of porphyrins and their applications to polariton chemistry (a review)

Porphyrins are a fundamental class of molecules involved in a multitude of biological and chemical functions ranging from photosynthesis in plants to biomarkers in medicine to optoelectronic devises. Despite the porphyrin molecule being such an important class of molecules known for centuries, its photophysics are surprisingly complex and models describing the spectroscopic behavior of porphyrins did not emerge until the 1950s. This review aims to distil the basics of porphyrin photophysics, describing how the Soret band and the Q band of the molecule are formed. In particular, a discussion of the four orbital theory and Hertzberg-Teller coupling will be conducted, both of which are necessary to understand the spectral properties of the porphyrin molecule. The review further aims to complement previous work discussing the chemical applications of hybrid light-matter states by discussing how the spectroscopic behavior of porphyrins is particularly useful in polariton chemistry.

Hybrid architectures for terahertz molecular polaritonics

Atoms and their different arrangements into molecules are nature’s building blocks. In a regime of strong coupling, matter hybridizes with light to modify physical and chemical properties, hence creating new building blocks that can be used for avant-garde technologies. However, this regime relies on the strong confinement of the optical field, which is technically challenging to achieve, especially at terahertz frequencies in the far-infrared region. Here we demonstrate several schemes of electromagnetic field confinement aimed at facilitating the collective coupling of a localized terahertz photonic mode to molecular vibrations. We observe an enhanced vacuum Rabi splitting of 200 GHz from a hybrid cavity architecture consisting of a plasmonic metasurface, coupled to glucose, and interfaced with a planar mirror. This enhanced light-matter interaction is found to emerge from the modified intracavity field of the cavity, leading to an enhanced zero-point electric field amplitude. Our study provides key insight into the design of polaritonic platforms with organic molecules to harvest the unique properties of hybrid light-matter states.

Assessing the Determinants of Cavity Polariton Relaxation Using Angle-Resolved Photoluminescence Excitation Spectroscopy.

The strong coupling of light and matter within electromagnetic resonators leads to the formation of cavity polaritons whose hybrid nature may help certain ground and excited state chemical processes. To help enable the development of polariton chemistry, we have developed and applied a spectroscopic technique to leverage the relatively larger spatial coherence of polaritons to assess the determinants of relaxation in hybrid light-matter states. By exciting the lower polariton (LP) state in cavity samples filled with different metalloporphyrin chromophores, we measured and modeled angle-resolved photoluminescence excitation spectra. Our results suggest that the shortest lived constituent of the LP state characterized by specific Hopfield coefficients limits the light absorption of the intracavity molecules, which we equate with the effective polariton lifetime. Our results suggest that researchers need to consider the lifetimes of both photons and excitons participating in strong light-matter coupling when designing polaritonic systems and the methods they can use to assess the relaxation of polaritonic states.

Polariton creation in coupled cavity arrays with spectrally disordered emitters

Integrated photonics has been a promising platform for analog quantum simulation of condensed matter phenomena in strongly correlated systems. To that end, we explore the implementation of all-photonic quantum simulators in coupled cavity arrays with integrated ensembles of spectrally disordered emitters. Our model is reflective of color center ensembles integrated into photonic crystal cavity arrays. Using the Quantum Master equation and the Effective Hamiltonian approaches, we study energy band formation and wavefunction properties in the open quantum Tavis–Cummings–Hubbard framework. We find conditions for polariton creation and (de)localization under experimentally relevant values of disorder in emitter frequencies, cavity resonance frequencies, and emitter-cavity coupling rates. To quantify these properties, we introduce two metrics, the polaritonic and nodal participation ratios, that characterize the light-matter hybridization and the node delocalization of the wavefunction, respectively. These new metrics combined with the Effective Hamiltonian approach prove to be a powerful toolbox for cavity quantum electrodynamical engineering of solid-state systems.

From weak to strong coupling: quasi-BIC metasurfaces for mid-infrared light-matter interactions.

Thanks to their giant, yet tunable, Q-factor resonances, all-dielectric metasurfaces supporting the quasi-bound states in the continuum (q-BIC) resonances are well-suited to provide a promising platform for quantum-coherent light-matter interactions. Yet, the strong coupling regime, characterized by the hybrid light-matter states - polaritons, has not yet been fully explored in the mid-infrared regime. This paper investigates the parameter space of vibrational strong coupling (VSC) between material and metasurface cavities supporting q-BIC resonances in the mid-infrared spectral range. We outline the effects of transition dipole strength, damping rate, and the number of molecules coupled to a single cavity, as well as the cavity damping rates, to understand their respective impacts on VSC. By tuning the Q-factor of the metasurface and material parameters, a new transition light-matter coupling zone is introduced, bridging the gap between weak and strong coupling, where polaritons form but their linewidths prohibit their spectral identification. The study further identifies the effects of cavity linewidth on polariton peak separability in strongly coupled systems, highlighting that the cavities with smaller nonradiative losses and narrower linewidths facilitate better polariton separability. Moreover, we found that matching cavity and material loss, satisfying the critical strong coupling condition, enhances the coupling strength between cavity and material. Overall, these findings can guide the design of photonic cavities suited for VSC experiments, contributing to the burgeoning fields of polaritonic chemistry, light-mediated modulation of chemical reactivity, and highly sensitive molecular spectroscopy.

Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling.

Strong coupling between photonic modes and molecular electronic excitations, creating hybrid light-matter states called polaritons, is an attractive avenue for controlling chemical reactions. Nevertheless, experimental demonstrations of polariton-modified chemical reactions remain sparse. Here, we demonstrate modified photoisomerization kinetics of merocyanine and diarylethene by coupling the reactant's optical transition with photonic microcavity modes. We leverage broadband Fourier-plane optical microscopy to noninvasively and rapidly monitor photoisomerization within microcavities, enabling systematic investigation of chemical kinetics for different cavity-exciton detunings and photoexcitation conditions. We demonstrate three distinct effects of cavity coupling: first, a renormalization of the photonic density of states, akin to a Purcell effect, leads to enhanced absorption and isomerization rates at certain wavelengths, notably red-shifting the onset of photoisomerization. This effect is present under both strong and weak light-matter couplings. Second, kinetic competition between polariton localization into reactive molecular states and cavity losses leads to a suppression of the photoisomerization yield. Finally, our key result is that in reaction mixtures with multiple reactant isomers, exhibiting partially overlapping optical transitions and distinct isomerization pathways, the cavity resonance can be tuned to funnel photoexcitations into specific reactant isomers. Thus, upon decoherence, polaritons localize into a chosen isomer, selectively triggering the latter's photoisomerization despite initially being delocalized across all isomers. This result suggests that careful tuning of the cavity resonance is a promising avenue to steer chemical reactions and enhance product selectivity in reaction mixtures.

A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron-Photon Correlation.

In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, vibrational polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a molecular quantum chemistry-based computational scheme for linear IR spectra of vibrational polaritons in polyatomic molecules, which perturbatively accounts for nonresonant electron-photon interactions under VSC. Specifically, we formulate a cavity Born-Oppenheimer perturbation theory (CBO-PT) linear response approach, which provides an approximate but systematic description of such electron-photon correlation effects in VSC scenarios while relying on molecular ab initio quantum chemistry methods. We identify relevant electron-photon correlation effects at the second order of CBO-PT, which manifest as static polarizability-dependent Hessian corrections and an emerging polarizability-dependent cavity intensity component providing access to transmission spectra commonly measured in vibro-polaritonic chemistry. Illustratively, we address electron-photon correlation effects perturbatively in IR spectra of CO2 and Fe(CO)5 vibro-polaritonic models in sound agreement with nonperturbative CBO linear response theory.

Coherent Interaction of a Few-Electron Quantum Dot with a Terahertz Optical Resonator.

We have investigated light-matter hybrid excitations in a quantum dot (QD) THz resonator coupled system. We fabricate a gate-defined QD near a THz split-ring resonator (SRR) by using a AlGaAs/GaAs two-dimensional electron system. By illuminating the system with THz radiation, the QD shows a current change whose spectrum exhibits coherent coupling between the electrons in the QD and the SRR as well as coupling between the two-dimensional electron system and the SRR. The latter coupling enters the ultrastrong coupling regime and the electron excitation in the QD also exhibits coherent coupling with the SRR with the remarkably large coupling constant, despite the fact that only a few electrons reside in the QD.