Strong Light-matter Coupling Research Articles

Cavity-Mediated Hybridization of Bright and Dark Excitons in an Ultrastrongly Coupled Carbon Nanotube Microcavity

Semiconducting single-walled carbon nanotubes (SWCNTs) are ideal materials for studying strong light–matter coupling and related polaritonic phenomena at room temperature. SWCNTs possess strong, re...

Self-Hybridized Polaritonic Emission from Layered Perovskites.

Light-matter coupling in excitonic materials has been the subject of intense recent investigations due to emergence of new materials. Two-dimensional layered hybrid organic/inorganic perovskites (2D HOIPs) support strongly bound excitons at room temperature with some of the highest oscillator strengths and electric loss tangents among the known excitonic materials. Here, we report strong light-matter coupling in Ruddlesden-Popper phase 2D HOIP crystals without the necessity of an external cavity. We report the concurrent occurrence of multiple orders of hybrid light-matter states via both reflectance and luminescence spectroscopy in thick (>100 nm) crystals and near-unity absorption in thin (<20 nm) crystals. We observe resonances with quality factors of >250 in hybridized exciton-polaritons and identify a linear correlation between exciton-polariton mode splitting and extinction coefficient of the various 2D HOIPs. Our work opens the door to studying polariton dynamics in self-hybridized and open cavity systems with broad applications in optoelectronics and photochemistry.

Plasmon polaritons in nanoparticle supercrystals: Microscopic quantum theory beyond the dipole approximation

Crystals of plasmonic metal nanoparticles have intriguing optical properties. They reach the regimes of ultrastrong and deep strong light-matter coupling, where the photonic states need to be included in the simulation of material properties. We propose a quantum description of the plasmon polaritons in supercrystals that starts from the dipole and quadrupole excitations of the nanoparticle building blocks and their coupling to photons. Our model excellently reproduces results of finite difference time domain simulations. It provides detailed insight into the emergence of the polariton states. Using the example of a face centered cubic crystals we show that the dipole and quadrupole states mix in many high symmetry directions of the Brilouin zone. A proper description of the plasmon and plasmon-polariton band structure is only possible when including the quadrupole-derived states. Our model leads to an expression of the reduced coupling strength in nanoparticle supercrystals that we show to enter the deep strong coupling regime for metal fill fractions above $0.8$. In addition to the plasmon-polariton energies we analyse the relative contributions of the dipole, quadrupole, and photonic states to their eigenfunctions and are able to demonstrate the decoupling of light in the deep strong coupling regime. Our results pave the way for a better understanding of the quantum properties of metallic nanoparticle supercrystals in the ultrastrong and deep-strong coupling regime.

Ultralong-Range Polariton-Assisted Energy Transfer in Organic Microcavities.

Non‐radiative energy transfer between spatially‐separated molecules in a microcavity can occur when an excitonic state on both molecules are strongly‐coupled to the same optical mode, forming so‐called “hybrid” polaritons. Such energy transfer has previously been explored when thin‐films of different molecules are relatively closely spaced (≈100 nm). In this manuscript, we explore strong‐coupled microcavities in which thin‐films of two J‐aggregated molecular dyes were separated by a spacer layer having a thickness of up to 2 μm. Here, strong light‐matter coupling and hybridisation between the excitonic transition is identified using white‐light reflectivity and photoluminescence emission. We use steady‐state spectroscopy to demonstrate polariton‐mediated energy transfer between such coupled states over “mesoscopic distances”, with this process being enhanced compared to non‐cavity control structures.

Enhanced optical nonlinearities under collective strong light-matter coupling

Optical microcavities and metallic nanostructures have been shown to significantly modulate the dynamics and spectroscopic response of molecular systems. We present a study of the nonlinear optics of a model consisting of $N$ anharmonic multilevel systems (e.g., Morse oscillators) undergoing collective strong coupling with a resonant infrared microcavity. We find that, under experimentally accessible conditions, molecular systems in microcavities may have nonlinear phenomena significantly intensified due to the high quality of polariton resonances and the enhanced microcavity electromagnetic energy density relative to free space. Particularly large enhancement of multiphoton absorption happens when multipolariton states are resonant with bare molecule multiphoton transitions. In particular, our model predicts two-photon absorption cross section enhancements by several orders of magnitude relative to free space when the Rabi splitting $\Omega_R$ is approximately equal to the molecular anharmonic shift $2\Delta$. Our results provide rough upper bounds to resonant nonlinear response enhancement factors as relaxation to dark states is treated phenomenologically. Notably, ensembles of two-level systems undergoing strong coupling with a cavity (described by the Tavis-Cummings model) show no such optical nonlinearity enhancements, highlighting the rich phenomenology afforded by multilevel anharmonic systems. Similar conclusions are expected to hold for excitonic systems that share features with our model (e.g., molecular dyes with accessible S_0 -> S_1 -> S_2 transitions) and strongly interact with a UV-visible cavity.

Top-emitting thermally activated delayed fluorescence organic light-emitting devices with weak light-matter coupling

Resonance interaction between a molecular transition and a confined electromagnetic field can lead to weak or strong light-matter coupling. Considering the substantial exciton–phonon coupling in thermally activated delayed fluorescence (TADF) materials, it is thus interesting to explore whether weak light-matter coupling can be used to redistribute optical density of states and to change the rate of radiative decay. Here, we demonstrate that the emission distribution of TADF emitters can be reshaped and narrowed in a top-emitting organic light-emitting device (OLED) with a weakly coupled microcavity. The Purcell effect of weak microcavity is found to be different for TADF emitters with different molecular orientations. We demonstrate that radiative rates of the TADF emitters with vertical orientation can be substantial increased in weakly coupled organic microcavity. These observations can enhance external quantum efficiencies, reduce efficiency roll-off, and improve color-purities of TADF OLEDs, especially for emitters without highly horizontal orientation.

Barrier-free reverse-intersystem crossing in organic molecules by strong light-matter coupling

Strong light-matter coupling provides the means to challenge the traditional rules of chemistry. In particular, an energy inversion of singlet and triplet excited states would be fundamentally remarkable since it would violate the classical Hund’s rule. An organic chromophore possessing a lower singlet excited state can effectively harvest the dark triplet states, thus enabling 100% internal quantum efficiency in electrically pumped light-emitting diodes and lasers. Here we demonstrate unambiguously an inversion of singlet and triplet excited states of a prototype molecule by strong coupling to an optical cavity. The inversion not only implies that the polaritonic state lies at a lower energy, but also a direct energy pathway between the triplet and polaritonic states is opened. The intrinsic photophysics of reversed-intersystem crossing are thereby completely overturned from an endothermic process to an exothermic one. By doing so, we show that it is possible to break the limit of Hund’s rule and manipulate the energy flow in molecular systems by strong light-matter coupling. Our results will directly promote the development of organic light-emitting diodes based on reversed-intersystem crossing. Moreover, we anticipate that it provides the pathway to the creation of electrically pumped polaritonic lasers in organic systems.

Analysis of the Forward and Reverse Strongly Coupled States on the Nonradiative Energy Transfer Effect.

Nonradiative energy transfer (NRET) under light-matter strong coupling interaction provides an efficient method to achieve the ultralong-distance and ultrafast energy transfer, which is of significance in realizing remote control chemistry and the real-time dynamic research of biological macromolecules interaction and so on. Here we show that not only can the cavity mode first resonate with the donor to form a cascade hybrid light-matter states to drive energy transfer, when the cavity mode first resonates with the acceptor, it also can enhance the nonradiative energy transfer between the donor and the acceptor. Importantly, although these two strong coupling systems can enhance energy transfer, the polariton-mediated energy transfer mechanism behind these processes is different. By employing the quantum Tavis-Cummings theory, we calculate the time evolution of the mean photon number of each polariton state to analyze the energy transfer effect under different strongly coupled states.

Direct Transition from Triplet Excitons to Hybrid Light-Matter States via Triplet-Triplet Annihilation.

Strong light–matter coupling generates hybrid states that inherit properties of both light and matter, effectively allowing the modification of the molecular potential energy landscape. This phenomenon opens up a plethora of options for manipulating the properties of molecules, with a broad range of applications in photochemistry and photophysics. In this article, we use strong light–matter coupling to transform an endothermic triplet–triplet annihilation process into an exothermic one. The resulting gradual on–off photon upconversion experiment demonstrates a direct conversion between molecular states and hybrid light–matter states. Our study provides a direct evidence that energy can relax from nonresonant low energy molecular states directly into hybrid light–matter states and lays the groundwork for tunable photon upconversion systems that modify molecular properties in situ by optical cavities rather than with chemical modifications.

Enhanced Scattering between Electrons and Exciton-Polaritons in a Microcavity.

The interplay between strong light-matter interactions and charge doping represents an important frontier in the pursuit of exotic many-body physics and optoelectronics. Here, we consider a simplified model of a two-dimensional semiconductor embedded in a microcavity, where the interactions between electrons and holes are strongly screened, allowing us to develop a diagrammatic formalism for this system with an analytic expression for the exciton-polariton propagator. We apply this to the scattering of spin-polarized polaritons and electrons, and show that this is strongly enhanced compared with exciton-electron interactions. As we argue, this counterintuitive result is a consequence of the shift of the collision energy due to the strong light-matter coupling, and hence this is a generic feature that applies also for more realistic electron-hole and electron-electron interactions. We furthermore demonstrate that the lack of Galilean invariance inherent in the light-matter coupled system can lead to a narrow resonancelike feature for polariton-electron interactions close to the polariton inflection point. Our results are potentially important for realizing tunable light-mediated interactions between charged particles.

Large Enhancement of Ferromagnetism under a Collective Strong Coupling of YBCO Nanoparticles.

Light–Matter strong coupling in the vacuum limit has been shown, over the past decade, to enhance material properties. Oxide nanoparticles are known to exhibit weak ferromagnetism due to vacancies in the lattice. Here we report the 700-fold enhancement of the ferromagnetism of YBa2Cu3O7–x nanoparticles under a cooperative strong coupling at room temperature. The magnetic moment reaches 0.90 μB/mol, and with such a high value, it competes with YBa2Cu3O7–x superconductivity at low temperatures. This strong ferromagnetism at room temperature suggest that strong coupling is a new tool for the development of next-generation magnetic and spintronic nanodevices.

Theoretical Study of Tunable Optical Resonators in Periodic and Quasiperiodic One-Dimensional Photonic Structures Incorporating a Nematic Liquid Crystal

In this work, the transfer matrix method (TMM) is employed to investigate the optical properties of one-dimensional periodic and quasiperiodic photonic crystals containing nematic liquid crystal (NLC) layers. This structure is expressed as (ABC)J(CBA)J and made of alternated layers of isotropic dielectrics SiO2 (A), BGO (B) and nematic liquid crystal (C). The simulation study shows that the proposed ternary configuration exhibits tunable defect mode within the photonic band gap (PBG) that can be manipulated by adjusting the thicknesses of NLC layers in order of the periodic lattice. In addition, the optimized structure permits for strong confinement light giving rise to an optical microcavity. The application of an applied voltage into NLC layers enables improving the sensitivity by guiding the local defect mode. It has been also shown that by applying quasiperiodic inflation according to Rudin Shapiro Sequence (RSS) scheme to main periodic structure, several tunable resonant modes appear within the PBG. The presence of such sharp resonant peaks reflects that the quasiperiodic NLC-based structure behaves like multiple microcavites with strong light-matter coupling.

Gauge freedom, quantum measurements, and time-dependent interactions in cavity QED

The interaction between the electromagnetic field inside a cavity and natural or artificial atoms has played a crucial role in developing our understanding of light-matter interaction, and is central to various quantum technologies. Recently, new regimes beyond the weak and strong light-matter coupling have been explored in several settings. These regimes, where the interaction strength is comparable (ultrastrong) or even higher (deep-strong) than the transition frequencies in the system, can give rise to new physical effects and applications. At the same time, they challenge our understanding of cavity QED. When the interaction strength is so high, fundamental issues like the proper definition of subsystems and of their quantum measurements, the structure of light-matter ground states, or the analysis of time-dependent interactions are subject to ambiguities leading to even qualitatively distinct predictions. The resolution of these ambiguities is also important for understanding and designing next-generation quantum devices that will exploit the ultrastrong coupling regime. Here we discuss and provide solutions to these issues.

Exciton-Exciton Interaction beyond the Hydrogenic Picture in a MoSe_{2} Monolayer in the Strong Light-Matter Coupling Regime.

In transition metal dichalcogenides' layers of atomic-scale thickness, the electron-hole Coulomb interaction potential is strongly influenced by the sharp discontinuity of the dielectric function across the layer plane. This feature results in peculiar nonhydrogenic excitonic states in which exciton-mediated optical nonlinearities are predicted to be enhanced compared to their hydrogenic counterparts. To demonstrate this enhancement, we perform optical transmission spectroscopy of a MoSe_{2} monolayer placed in the strong coupling regime with the mode of an optical microcavity and analyze the results quantitatively with a nonlinear input-output theory. We find an enhancement of both the exciton-exciton interaction and of the excitonic fermionic saturation with respect to realistic values expected in the hydrogenic picture. Such results demonstrate that unconventional excitons in MoSe_{2} are highly favorable for the implementation of large exciton-mediated optical nonlinearities, potentially working up to room temperature.

Evolutionary optimization of light-matter coupling in open plasmonic cavities.

Using a particle swarm optimization algorithm and finite-difference in time-domain simulations, we optimize the coupling strength between excitons in poly(3-hexylthiophene-2,5-diyl) (P3HT) and surface lattice resonances in open cavities defined by arrays of aluminum nanoparticles. Strong light-matter coupling and the formation of exciton-polaritons are demonstrated. Nanoparticle arrays with optimal dimensions have been fabricated and measured, validating the predictions by the numerical method. P3HT is a regioregular semiconducting polymer used as a donor material in acceptor-donor blends for organic photovoltaic applications. Our results demonstrate the efficacy of the proposed method for the optimization of light-matter coupling and its potential application for the enhanced performance of optoelectronic devices.

Cavity-assisted preparation and detection of a unitary Fermi gas

We report on the fast production and weakly destructive detection of a Fermi gas with tunable interactions in a high finesse cavity. The cavity is used both with far off-resonant light to create a deep optical dipole trap, and with near-resonant light to reach the strong light–matter coupling regime. The cavity-based dipole trap allows for an efficient capture of laser-cooled atoms, and the use of a lattice-cancellation scheme makes it possible to perform efficient intra-cavity evaporative cooling. After transfer in a crossed optical dipole trap, we produce deeply degenerate unitary Fermi gases with up to 7 × 105 atoms inside the cavity, with an overall 2.85 s long sequence. The cavity is then probed with near-resonant light to perform five hundred-times repeated, dispersive measurements of the population of individual clouds, allowing for weakly destructive observations of slow atom-number variations over a single sample. This platform will make possible the real-time observation of transport and dynamics as well as the study of driven-dissipative, strongly correlated quantum matter.

Understanding radiative transitions and relaxation pathways in plexcitons

Summary Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.

„Ostry metal”, czyli od piorunochronu do oddziaływania światło–materia w pikownękach

Light is a valuable source of information of the surrounding world as a consequence of light–matter interactions.One of the major challenges in contemporary science is shaping those interactions. In this article, I present a method of reaching strong light–matter coupling regime using optical cavities with special focus on the case of plasmonic picocavities, which are formed by sharp metallic features.

Multi-scale dynamics simulations of molecular polaritons: The effect of multiple cavity modes on polariton relaxation.

Coupling molecules to the confined light modes of an optical cavity is showing great promise for manipulating chemical reactions. However, to fully exploit this principle and use cavities as a new tool for controlling chemistry, a complete understanding of the effects of strong light-matter coupling on molecular dynamics and reactivity is required. While quantum chemistry can provide atomistic insight into the reactivity of uncoupled molecules, the possibilities to also explore strongly coupled systems are still rather limited due to the challenges associated with an accurate description of the cavity in such calculations. Despite recent progress in introducing strong coupling effects into quantum chemistry calculations, applications are mostly restricted to single or simplified molecules in ideal lossless cavities that support a single light mode only. However, even if commonly used planar mirror micro-cavities are characterized by a fundamental mode with a frequency determined by the distance between the mirrors, the cavity energy also depends on the wave vector of the incident light rays. To account for this dependency, called cavity dispersion, in atomistic simulations of molecules in optical cavities, we have extended our multi-scale molecular dynamics model for strongly coupled molecular ensembles to include multiple confined light modes. To validate the new model, we have performed simulations of up to 512 Rhodamine molecules in red-detuned Fabry-Pérot cavities. The results of our simulations suggest that after resonant excitation into the upper polariton at a fixed wave vector, or incidence angle, the coupled cavity-molecule system rapidly decays into dark states that lack dispersion. Slower relaxation from the dark state manifold into both the upper and lower bright polaritons causes observable photo-luminescence from the molecule-cavity system along the two polariton dispersion branches that ultimately evolves toward the bottom of the lower polariton branch, in line with experimental observations. We anticipate that the more realistic cavity description in our approach will help to better understand and predict how cavities can modify molecular properties.

Altering intermolecular forces with optical cavities

QED methodologies from first principles show that strong light-matter coupling inside an optical cavity could be used to alter intermolecular forces within large molecular systems.