Organic Polariton Research Articles

A highly stable and efficient organic microcavity polariton laser

With their remarkably low thresholds, organic polariton lasers are a promising alternative to organic photonic lasers. However, device stability remains a challenge, in part due to material degradation during deposition of the top dielectric mirror. We demonstrate polariton lasers based on 4,4′-Bis(4-(9H-carbazol-9-yl)styryl)biphenyl (BSBCz) as active material that achieve a low lasing threshold of 8.7 μJ/cm2, and we show that a ZrO2 protection layer between active layer and top mirror significantly improves stability. Optimized devices exhibit minimal degradation after 100,000 excitation pulses at 3.8 times above threshold. Our findings establish BSBCz as an attractive candidate for future injection driven polariton lasers.Graphical abstract

Non-Hermitian molecular dynamics simulations of exciton-polaritons in lossy cavities.

The observation that materials can change their properties when placed inside or near an optical resonator has sparked a fervid interest in understanding the effects of strong light-matter coupling on molecular dynamics, and several approaches have been proposed to extend the methods of computational chemistry into this regime. Whereas the majority of these approaches have focused on modeling a single molecule coupled to a single cavity mode, changes to chemistry have so far only been observed experimentally when very many molecules are coupled collectively to multiple modes with short lifetimes. While atomistic simulations of many molecules coupled to multiple cavity modes have been performed with semi-classical molecular dynamics, an explicit description of cavity losses has so far been restricted to simulations in which only a very few molecular degrees of freedom were considered. Here, we have implemented an effective non-Hermitian Hamiltonian to explicitly treat cavity losses in large-scale semi-classical molecular dynamics simulations of organic polaritons and used it to perform both mean-field and surface hopping simulations of polariton relaxation, propagation, and energy transfer.

Controlling the Spatial Profile and Energy Landscape of Organic Polariton Condensates in Double-Dye Cavities.

The development of high-speed, all-optical polariton logic devices underlies emerging unconventional computing technologies and relies on advancing techniques to reversibly manipulate the spatial extent and energy of polartion condensates. We investigate active spatial control of polariton condensates independent of the polariton, gain-inducing excitation profile. This is achieved by introducing an extra intracavity semiconductor layer, nonresonant to the cavity mode. Partial saturation of the optical absorption in the uncoupled layer enables the ultrafast modulation of the effective refractive index and, through excited-state absorption, the polariton dissipation. Utilizing an intricate interplay of these mechanisms, we demonstrate control over the spatial profile, density, and energy of a polariton condensate at room temperature.

Multi-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling

Exciton transport can be enhanced in the strong coupling regime where excitons hybridize with confined light modes to form polaritons. Because polaritons have group velocity, their propagation should be ballistic and long-ranged. However, experiments indicate that organic polaritons propagate in a diffusive manner and more slowly than their group velocity. Here, we resolve this controversy by means of molecular dynamics simulations of Rhodamine molecules in a Fabry-Pérot cavity. Our results suggest that polariton propagation is limited by the cavity lifetime and appears diffusive due to reversible population transfers between polaritonic states that propagate ballistically at their group velocity, and dark states that are stationary. Furthermore, because long-lived dark states transiently trap the excitation, propagation is observed on timescales beyond the intrinsic polariton lifetime. These insights not only help to better understand and interpret experimental observations, but also pave the way towards rational design of molecule-cavity systems for coherent exciton transport.

Optical gain and photo-bleaching of organic dyes, quantum dots, perovskite nanoplatelets and nanodiamonds

ABSTRACT Optical gain and resistance against photo-bleaching are key material parameters for practical applications in microlasers and microphotonics. Here, we present studies of optical amplification and photo-bleaching in a wide range of optical gain materials, including fluorescent dyes, quantum dots and rods, organic and inorganic room temperature polaritons, and nanodiamonds with emission range from 430 to 680 nm. We used amplified spontaneous emission (ASE) for each material to measure the optical gain. Robustness against photo-bleaching was determined by measuring the intensity of spontaneous emission of the material as a function of the number of excitation femtosecond pulses (106–1010) at various excitation energy densities. We show that pyrromethene laser dyes are the best organic emitters in terms of low excitation energy and good optical gain, whereas solid-state polariton materials are better in terms of high optical gain and stability. We found that all organic and inorganic optical gain materials bleach completely after 106–109 illumination pulses with typical 0.1–0.6 GW/cm2 peak power density, with an exception of nanodiamonds. We show that nanodiamonds are the only optical gain material that shows no photo-bleaching beyond the 1010 excitation pulses of 300 fs pulse duration and with 0.16 GW/cm2 peak power density.

Fate of the upper polariton: Breakdown of the quasiparticle picture in the continuum

Organic polaritons resulting from the strong hybridisation between photons and matter excitations have arisen as a suitable platform to device light-matter technological interfaces at room temperature. Despite their inherent complexity, organic polaritons are commonly regarded as coherent light-matter excitations that can be described in terms of Landau's quasiparticle approach. Here, we experimentally unveil the role of incoherent matter excitations on the polaritons by exploring the relevant energy-momentum parameter space. We demonstrate the emergence of a well-defined lower polariton branch and an intriguing fading of the upper polariton at its entrance to a continuum of matter excitations. This marks the breakdown of the simplistic quasiparticle picture for this branch and the formation of a more complex quantum state. Our experimental results are sustained by a general theoretical framework that allows understanding the light-matter hybridisation beyond the quasiparticle approach. Our work expands the understanding of organic polaritons in all their complexity and increases their technological significance.

Light-responsive organic polaritons from first principles.

Controlling the optical properties of light-responsive organic molecules is essential for their application in photonics. We demonstrate how light-responsive organic polaritons formed inside an optical cavity can be used to modify these properties based on first principles. Specifically, we study the excited state properties of the trans-azobenzene molecule and the free base tetraphenyl porphyrin (H2TPP) molecule under weak to strong light-matter coupling. Our results show that the cavity can modulate the dispersion and absorption properties of organic molecules. Compared to the case outside the cavity, the anomalous dispersion of the trans-azobenzene molecule inside the cavity is suppressed and this suppression decreases with increasing coupling strength, showing the potential of strong light-matter coupling in manipulating the optical dipole trap of organic molecules. Moreover, by adjusting the cavity parameters to tune the strength of the light-matter coupling, we achieve free switching between symmetric Lorentz and asymmetric Fano line shapes for H2TPP polaritonic excitations. During the switching between these spectral features, we also find that the cavity can be used to control the spontaneous radiation of organic molecules via the Purcell effect. These findings provide a new pathway to manipulate the optical properties of light-responsive organic molecules.

Mode switching dynamics in organic polariton lasing

We study the dynamics of multimode polariton lasing in organic microcavities by using a second-order cumulant equation approach. By inspecting the time evolution of the photon mode occupations, we show that if multiple lasing peaks are observed in time-integrated mode occupations, the reason can be either bi-modal lasing or temporal switching between several modes. The former takes place within a narrow range of parameters while the latter occurs more widely. We find that the origin of the temporal switching is different in the weak- and strong-coupling regimes. At weak coupling slope efficiency is the determining factor, while for strong coupling it is changes in the eigenmodes and gain spectrum upon pumping. This difference is revealed by investigating the photoluminescence and momentum-resolved gain spectra. Our results underscore the importance of understanding the time evolution of the populations when characterizing the lasing behaviour of a multimode polariton system, and show how these features differ between weak and strong coupling.

Organic charged polaritons in the ultrastrong coupling regime

We embedded an all-hydrocarbon-based carbocation in a metallic microcavity that was tuned to resonance with an electronic transition of the carbocation. The measured Rabi splitting was 41% of the excitation energy, putting the system well into the ultrastrong coupling regime. Importantly, due to the intrinsic charge on the carbocation, the polaritons that form carry a significant charge fraction $0.55 e_0$ and a large charge-to-mass ratio ($\sim 2400 e_0 / m_0$). Moreover, the ground state of the ultrastrongly coupled system is calculated to carry about one percent of one elementary charge, implying a potentially enhanced charge transport across the molecules. These unique properties of our system, together with its convenient preparation, provide a practical platform to study charged polaritons in the ultrastrong coupling regime.

Thermalization of Fluorescent Protein Exciton-Polaritons at Room Temperature.

Fluorescent proteins (FPs) have recently emerged as a serious contender for realizing ultralow threshold room temperature exciton-polariton condensation and lasing. This contribution investigates the thermalization of FP microcavity exciton-polaritons upon optical pumping under ambient conditions. Polariton cooling is realized using a new FP molecule, called mScarlet, coupled strongly to the optical modes in a Fabry-Pérot cavity. Interestingly, at the threshold excitation energy (fluence) of ≈9 nJ per pulse (15.6 mJ cm-2 ), an effective temperature is observed, Teff ≈ 350 ± 35 K close to the lattice temperature indicative of strongly thermalized exciton-polaritons at equilibrium. This efficient thermalization results from the interplay of radiative pumping facilitated by the energetics of the lower polariton branch and the cavity Q-factor. Direct evidence for dramatic switching from an equilibrium state into a metastable state is observed for the organic cavity polariton device at room temperature via deviation from the Maxwell-Boltzmann statistics at k‖ = 0 above the threshold. Thermalized polariton gases in organic systems at equilibrium hold substantial promise for designing room temperature polaritonic circuits, switches, and lattices for analog simulation.

Dispersion of organic exciton polaritons—a novel undergraduate experiment

We report on an innovative and simple way to perform an experiment which utilizes the properties of a quantized electromagnetic field coupled to Frenkel excitons in organic materials, forming exciton–polaritons (EP). We present an optical setup, which allowed to perform precise measurements of transmission of organic optical cavities at different angles of incidence and to study the dispersion relation of EP. We provided the full theoretical background of EP and demonstrated that the experimental results are in good agreement with theoretical predictions. Furthermore, we extracted the strong coupling strength and the excitonic–photonic weights of organic cavity samples.

Polariton condensation in a microcavity using a highly-stable molecular dye

We have fabricated organic polariton microcavities that exhibit remarkable photostability, even in the condensation regime.

Enhanced Light–Matter Interaction and Polariton Relaxation by the Control of Molecular Orientation

AbstractExciton‐polaritons, in which the electronic state of an excited organic molecule and a photonic state are strongly coupled, can form a Bose–Einstein condensate (BEC) at room temperature. However, so far, the reported thresholds of organic polariton BECs under optical excitation are as high asPth = 11–500 μJ cm–2. One route toward lowering the condensation threshold is to increase the Rabi energy by aligning the molecular transition dipole moments. In this report, it is demonstrated that control of the orientation of a perylene‐based discotic dye, which is able to self‐organize in mesogenic columnar structures, can significantly enhance exciton–photon interaction and polariton relaxation rate in optical cavities. These results show the importance of the molecular orientation for strong light–matter interactions and provide a promising strategy toward the realization of an organic low threshold polariton BEC system and electrically driven organic polariton BEC.

Strong light–matter interaction in organic microcavity polaritons: essential criteria, design principles and typical configurations

Strong light–matter interaction in organic microcavity polaritons: essential criteria, design principles and typical configurations

Mechanisms for nonlinear refractive index in organic cavity polaritons

The nonlinear optical response of organic polaritonic matter has received increasing attention due to their enhanced and controllable nonlinear response and their potential for novel optical devices such as compact photon sources and optical and quantum information devices. Using $z$ scans at different wavelengths and incident powers we have studied the nonlinear optical dispersion of ultrastrongly coupled organic cavity polaritons near the lower polariton band. We show that the up to 150-fold enhancement of the nonlinear response compared to a cavityless organic film arises from an intensity-dependent polaritonic resonant frequency shift (``blueshift''). Consequently, we find that these $z$-scan data can only be described by several terms of a power series expansion in intensity whose respective contributions depend on power broadening and detuning from the lower polariton band. We further show that the nonlinear response can be quantitatively described by a semiclassical three-level molecular model coupled to the cavity in which saturation reduces the Rabi splitting, thus accounting for the lower polariton band's observed blueshift.

Anisotropic light-matter coupling and below-threshold excitation dynamics in an organic crystal microcavity.

Organic semiconductors are promising candidates as platforms for room temperature polaritonic devices. An issue for practical implementation of organic polariton devices is the lowering of condensation threshold. Here we investigate anisotropic light-matter coupling characteristics in an organic crystal microcavity showing strong molecular orientation. Furthermore, the below-threshold excitation dynamics are investigated to clarify the spontaneous transition pathways from reservoir to polariton states. Time-resolved photoluminescence measurements reveal that photonic/excitonic hybrid transition processes coexist in the microcavity system. This finding provides valuable insights into a detailed understanding of polariton dynamics and help in the design of polaritonic devices showing a low-threshold condensed phase.

Low Threshold Room Temperature Polariton Lasing from Fluorene‐Based Oligomers

AbstractOrganic semiconductors possessing tightly bound Frenkel excitons are known to be attractive candidates for demonstrating polariton lasing at room temperature. As polariton lasing can occur without inversion, it is a potential route to very low threshold coherent light sources. However, so far, the thresholds of organic polariton lasers have generally been much higher than those of organic photon lasers. Here this problem has been addressed by investigating two new organic molecules with a structure combining fluorene and carbazole groups. The materials are readily deposited from solution and exhibit high photoluminescence quantum yields, high absorption coefficients, and large radiative decay rates in neat films. Room temperature polariton lasing is realized in both materials with incident thresholds of 13.5 and 9.7 µJ cm−2, corresponding to absorbed thresholds of 3.3 and 2.2 µJ cm−2, respectively. These are the lowest values reported to date for polariton lasing in organic semiconductor materials, and approach typical values for organic photon lasers. The step‐like power dependent blue‐shift of polariton modes indicates an interplay between different depletion channels of the exciton reservoir. This work brings practical room temperature polaritonic devices and future realization of electrically driven polariton lasers a step closer.

Room temperature exciton\u2013polariton Bose\u2013Einstein condensation in organic single-crystal microribbon cavities

Exciton–polariton Bose–Einstein condensation (EP BEC) is of crucial importance for the development of coherent light sources and optical logic elements, as it creates a new state of matter with coherent nature and nonlinear behaviors. The demand for room temperature EP BEC has driven the development of organic polaritons because of the large binding energies of Frenkel excitons in organic materials. However, the reliance on external high-finesse microcavities for organic EP BEC results in poor compactness and integrability of devices, which restricts their practical applications in on-chip integration. Here, we demonstrate room temperature EP BEC in organic single-crystal microribbon natural cavities. The regularly shaped microribbons serve as waveguide Fabry–Pérot microcavities, in which efficient strong coupling between Frenkel excitons and photons leads to the generation of EPs at room temperature. The large exciton–photon coupling strength due to high exciton densities facilitates the achievement of EP BEC. Taking advantages of interactions in EP condensates and dimension confinement effects, we demonstrate the realization of controllable output of coherent light from the microribbons. We hope that the results will provide a useful enlightenment for using organic single crystals to construct miniaturized polaritonic devices.

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.

Simulating photodissociation reactions in bad cavities with the Lindblad equation.

Optical cavities, e.g., as used in organic polariton experiments, often employ low finesse mirrors or plasmonic structures. The photon lifetime in these setups is comparable to the timescale of the nuclear dynamics governing the photochemistry. This highlights the need for including the effect of dissipation in the molecular simulations. In this study, we perform wave packet dynamics with the Lindblad master equation to study the effect of a finite photon lifetime on the dissociation of the MgH+ molecule model system. Photon lifetimes of several different orders of magnitude are considered to encompass an ample range of effects inherent to lossy cavities.