Lower Polariton Research Articles

Direct extraction of optical constants of organic semiconductors in ultrastrongly coupled microcavities and their application in antireflection design for polariton devices

The strongly bound Frenkel excitons in organic semiconductors enable strong or even ultrastrong exciton-photon coupling in room-temperature cavities, with the resulting polariton states typically resolved through reflectance measurements. This paper demonstrates that the distinct features of exciton and polariton modes in the reflectance spectra of strongly/ultrastrongly coupled organic microcavities can be effectively utilized to extract the optical constants and physical thickness of the embedded organic semiconductor. We investigate metal-clad microcavities based on two prototype conjugated polymers, poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT), both exhibiting ultrastrong coupling characteristics. The (n,k) spectra and thickness of these polymer films are determined by fitting the normal incidence reflectance spectra of organic microcavities, using Kramers-Kronig transformation and transfer-matrix calculations with varying optical and thickness parameters. We also examine the individual effects of the main fitting parameters on the spectrum, establishing a close correlation with the underlying polariton properties. Moreover, we analyze the optical admittance at exciton and polariton modes to understand reflectance variations with different parameters, which facilitates precise control of optical properties at specific modes through cavity design. Finally, using the extracted optical constants of MDMO-PPV and P3HT, we propose optimized microcavity designs that exhibit antireflection at the lower polariton mode for potential luminescence and photodetection device applications.

Circumventing the polariton bottleneck via dark excitons in 2D semiconductors

Efficient scattering into the exciton polariton ground state is a key prerequisite for generating Bose–Einstein condensates and low-threshold polariton lasing. However, this can be challenging to achieve at low densities due to the polariton bottleneck effect that impedes phonon-driven scattering into low-momentum polariton states. The rich exciton landscape of transition metal dichalcogenides (TMDs) provides potential intervalley scattering pathways via dark excitons to rapidly populate these polaritons. Here, we present a theoretical and fully microscopic study exploring the time- and momentum-resolved relaxation of exciton polaritons supported by a MoSe2 monolayer integrated within a Fabry–Perot cavity. By exploiting phonon-assisted transitions between momentum-dark excitons and the lower polariton branch, we demonstrate that it is possible to circumvent the bottleneck region and efficiently populate the polariton ground state. Furthermore, this intervalley pathway is predicted to give rise to, yet unobserved, angle-resolved phonon sidebands in low-temperature photoluminescence spectra that are associated with momentum-dark excitons. This represents a distinct signature for efficient phonon-mediated polariton-dark-exciton interactions.

Non-equilibrium rate theory for polariton relaxation dynamics.

We derive an analytic expression of the non-equilibrium Fermi's golden rule (NE-FGR) expression for a Holstein-Tavis-Cumming Hamiltonian, a universal model for many molecules collectively coupled to the optical cavity. These NE-FGR expressions capture the full-time-dependent behavior of the rate constant for transitions from polariton states to dark states. The rate is shown to be reduced to the well-known frequency domain-based equilibrium Fermi's golden rule (E-FGR) expression in the equilibrium and collective limit and is shown to retain the same scaling with the number of sites in non-equilibrium and non-collective cases. We use these NE-FGR to perform population dynamics with a time-non-local and time-local quantum master equation and obtain accurate population dynamics from the initially occupied upper or lower polariton states. Furthermore, NE-FGR significantly improves the accuracy of the population dynamics when starting from the lower polariton compared to the E-FGR theory, highlighting the importance of the non-Markovian behavior and the short-time transient behavior in the transition rate constant.

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.

Polariton-polariton interaction induced by the hopping effect between two monolayers

Investigating the quantum many-body interaction in microcavity semiconductor systems is a significant objective in current research. Hence, in this study, Green’s function was employed to investigate the hopping effect between two monolayers denoted as L and R. The interaction between excitons in L monolayer and R monolayer, characterized by spin-like properties, leads to the generation of Josephson currents and emergence of two quasiparticle branches, known as LP+ and LP− polaritons (i.e., two low polariton states). And compared with other papers, such as reference 5, the research shows that presence of hopping interaction and many-body interaction between monolayers causes significant enhancement phenomenon of residue Z, which will further reduce the effective mass. This is more conducive to Bose–Einstein condensates (BEC). Furthermore, we investigated the Parity-Time symmetry (PT symmetry) of the system. The PT broken phase transition point will appear when the condition of PT symmetry is satisfied.

Theory and quantum dynamics simulations of exciton-polariton motional narrowing.

The motional narrowing effect has been extensively studied for cavity exciton-polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior and (2) the asymmetric linewidths for the upper polariton and the lower polariton. However, a minimal theoretical model that is clear and adequate to address all these effects as well as the linewidth scaling relations remains missing. In this work, based on the single mode 1D Holstein-Tavis-Cummings (HTC) model, we studied the motional narrowing effect of the polariton linear absorption spectra via both semi-analytic derivations and numerically exact quantum dynamics simulations using the hierarchical equations of motion approach. The results reveal that under collective light-matter coupling between a cavity mode and N molecules, the polariton linewidth scales as 1/N under the slow limit, while scales as 1/N under the fast limit, due to the polaron decoupling effect. Furthermore, by varying the detunings, the polariton linewidths exhibit significant motional narrowing, covering both characters mentioned above. Our analytic linewidth expressions [Eqs. (34) and (35)] agree well with the numerical exact simulations in all the parameter regimes we explored. These results indicate that the physics of motional narrowing is adequately accounted for by the single-mode 1D HTC model. We envision that both the numerical results and the analytic polariton linewidths expression presented in this work will offer great theoretical value for providing a better understanding of the exciton-polariton motional narrowing based on the HTC model.

Cavity Controlled Upconversion in CdSe Nanoplatelet Polaritons.

Exciton-polaritons provide a versatile platform for investigating quantum electrodynamics effects in chemical systems, such as polariton-altered chemical reactivity. However, using polaritons in chemical contexts will require a better understanding of their photophysical properties under ambient conditions, where chemistry is typically performed. Here, we used cavity quality factor to control strong light-matter interactions and in particular the excited state dynamics of colloidal CdSe nanoplatelets (NPLs) coupled to a Fabry-Pérot optical cavity. With increasing cavity quality factor, we observe significant population of the upper polariton (UP) state, exemplified by the rare observation of substantial UP photoluminescence (PL). Excitation of the lower polariton (LP) states results in upconverted PL emission from the UP branch due to efficient exchange of population between the LP, UP and the reservoir of dark states present in collectively coupled polaritonic systems. In addition, we measure time scales for polariton dynamics ∼100 ps, implying great potential for NPL based polariton systems to affect photochemical reaction rates. State-of-the-art quantum dynamical simulations show outstanding quantitative agreement with experiments, and thus provide important insight into polariton photophysical dynamics of collectively coupled nanocrystal-based systems. These findings represent a significant step toward the development of practical polariton photochemistry platforms.

Dark State Concentration Dependent Emission and Dynamics of CdSe Nanoplatelet Exciton-Polaritons.

The recent surge of interest in polaritons has prompted fundamental questions about the role of dark states in strong light-matter coupling phenomena. Here, we systematically vary the relative number of dark states by controlling the number of stacked CdSe nanoplatelets confined in a Fabry-Pérot cavity. We find the emission spectrum to change significantly with an increasing number of nanoplatelets, with a gradual shift of the dominant emission intensity from the lower polariton branch to a manifold of dark states. Through accompanying calculations based on a kinetic model, this shift is rationalized by an entropic trapping of excitations by the dark state manifold, while a weak dark state dispersion due to local disorder explains their nonzero emission. Our results point toward the relevance of the dark state concentration to the optical and dynamical properties of cavity-embedded quantum emitters with ramifications for Bose-Einstein condensate formation, polariton lasing, polariton-based quantum transduction schemes, and polariton chemistry.

Molecular Strong Coupling and Cavity Finesse.

Molecular strong coupling offers exciting prospects in physics, chemistry, and materials science. While attention has been focused on developing realistic models for the molecular systems, the important role played by the entire photonic mode structure of the optical cavities has been less explored. We show that the effectiveness of molecular strong coupling may be critically dependent on cavity finesse. Specifically we only see emission associated with a dispersive lower polariton for cavities with sufficient finesse. By developing an analytical model of cavity photoluminescence in a multimode structure we clarify the role of finite-finesse in polariton formation and show that lowering the finesse reduces the extent of the mixing of light and matter in polariton states. We suggest that the detailed nature of the photonic modes supported by a cavity will be as important in developing a coherent framework for molecular strong coupling as the inclusion of realistic molecular models.

Ultrafast Dynamics of Bloch Surface Wave Polaritons in Large-Area 2D Semiconductor Monolayers at Room Temperature.

The dynamics of strongly coupled polariton systems integrated with 2D transition metal dichalcogenides (TMDs) is key to enabling efficient coherent processes and achieving high-performance TMD-based polaritonic devices, such as ultralow-threshold polariton lasers and ultrafast optical switches. However, there has been a lack of a comprehensive understanding of the excited state dynamics in TMD-based polariton systems. In this work, ultrafast pump-probe optical spectroscopy is used to investigate the room temperature dynamics of the polariton systems consisting of TMD monolayer excitons strongly coupled with Bloch surface waves (BSWs) supported by all-dielectric photonic structures. The transient response is found for both above-exciton energy pumping and polariton-resonant pumping. The excited state population and ultrafast coherent coupling of the exciton reservoir and lower polariton (LP) branch are observed for resonant pumping. Moreover, it is found that the transient response of the LP first decays on a short-time scale of 0.15-0.25ps compared to the calculated intrinsic lifetime of 0.11-0.20ps, and is followed by a longer decay (>100ps) due to the dynamical evolution of the exciton reservoir. The results provide a fundamental understanding of the dynamics of TMD-based polariton systems while showing the potential for achieving efficient coherent optical processes for device applications.

Optical Emission Spectra of Molecular Excitonic Polariton Computed at the First‐Principles Level QED‐TDDFT

In microcavity, strong coupling between light and molecules leads to the formation of hybrid excitations, i.e., the polaritons, or exciton‐polaritons. Such coupling may alter the energy landscape of the system and the optical properties of the material, making it an effective approach for controlling the light emission from molecular materials. However, due to the complexity of vibrational modes, spectroscopic calculations for organic exciton‐polaritons remain to be challenging. In this work, based on the linear‐response quantum‐electrodynamical time‐dependent density functional theory (QED‐TDDFT), we employ the thermal vibrational correlation function (TVCF) formalism to calculate the molecular optical spectrum of the lower polaritons (LP) at first‐principles level for three molecules, i.e., anthracene, distyrylbenzenes (DSB), and rubrene. The polaron decoupling effect is confirmed from our first‐principles computations. The theoretical emission spectra of LP provide fruitful insights for molecular and device design in microcavities that are otherwise hindered due to the lack of vibrational information.

Room-temperature strong coupling between CdSe nanoplatelets and a metal-DBR Fabry-Pérot cavity.

The generation of exciton-polaritons through strong light-matter interactions represents an emerging platform for exploring quantum phenomena. A significant challenge in colloidal nanocrystal-based polaritonic systems is the ability to operate at room temperature with high fidelity. Here, we demonstrate the generation of room-temperature exciton-polaritons through the coupling of CdSe nanoplatelets (NPLs) with a Fabry-Pérot optical cavity, leading to a Rabi splitting of 74.6meV. Quantum-classical calculations accurately predict the complex dynamics between the many dark state excitons and the optically allowed polariton states, including the experimentally observed lower polariton photoluminescence emission, and the concentration of photoluminescence intensities at higher in-plane momenta as the cavity becomes more negatively detuned. The Rabi splitting measured at 5K is similar to that at 300K, validating the feasibility of the temperature-independent operation of this polaritonic system. Overall, these results show that CdSe NPLs are an excellent material to facilitate the development of room-temperature quantum technologies.

Theory of phonon sidebands in the absorption spectra of moiré exciton–polaritons

Excitons in twisted bilayers of transition metal dichalcogenides have strongly modified dispersion relations due to the formation of periodic moiré potentials. The strong coupling to a light field in an optical cavity leads to the appearance of moiré polaritons. In this paper, we derive a theoretical model for the linear absorption spectrum of the coupled moiré polariton–phonon system based on the time-convolutionless (TCL) approach. Results obtained by numerically solving the TCL equation are compared to those obtained in the Markovian limit and from a perturbative treatment of non-Markovian corrections. A key quantity for the interpretation of the findings is the generalized phonon spectral density. We discuss the phonon impact on the spectrum for realistic moiré exciton dispersions by varying twist angle and temperature. Key features introduced by the coupling to phonons are broadenings and energy shifts of the upper and lower polariton peak and the appearance of phonon sidebands between them. We analyze these features with respect to the role of Markovian and non-Markovian effects and find that they strongly depend on the twist angle. We can distinguish between the regimes of large, small, and intermediate twist angles. In the latter phonon effects are particularly pronounced due to dominating phonon transitions into regions which are characterized by van Hove singularities in the density of 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.

Ultrafast Spectroscopy under Vibrational Strong Coupling in Diphenylphosphoryl Azide.

Strong coupling of cavity photons and molecular vibrations creates vibrational polaritons that have been shown to modify chemical reactivity and alter material properties. While ultrafast spectroscopy of vibrational polaritons has been performed intensively in metal complexes, ultrafast dynamics in vibrationally strongly coupled organic molecules remain unexplored. Here, we report ultrafast pump-probe measurement and two-dimensional infrared spectroscopy in diphenylphosphoryl azide under vibrational strong coupling. Early time oscillatory structures indicate coherent energy exchange between the two polariton modes, which decays in ∼2 ps. We observe a large transient absorptive feature around the lower polariton, which can be explained by the overlapped excited-state absorption and derivative-shaped structures around the lower and upper polaritons. The latter feature is explained by the Rabi splitting contraction, which is ascribed to a reduced population in the ground state. These results reassure the previously reported spectroscopic theory to describe nonlinear spectroscopy of vibrational polaritons. We have also noticed the influence of the complicated layer structure of the cavity mirrors. The penetration of the electric field distribution into the layered structure of the dielectric-mirror cavities can significantly affect the Rabi splitting and the decay time constant of polaritonic systems.

Motional Narrowing through Photonic Exchange: Rational Suppression of Excitonic Disorder from Molecular Cavity Polariton Formation.

Maximizing the coherence between the constituents of molecular materials remains a crucial goal toward the implementation of these systems into everyday optoelectronic technologies. Here we experimentally assess the ability of strong light-matter coupling in the collective limit to reduce energetic disorder using porphyrin-based chromophores in Fabry-Pérot (FP) microresonator structures. Following characterization of cavity polaritons formed from chemically distinct porphyrin dimers, we find that the peaks corresponding to the lower polariton (LP) state in each sample do not possess widths consistent with conventional theories. We model the behavior of the polariton peak widths effectively using the results of spectroscopic theory. We correlate differences in the suppression of excitonic energetic disorder between our samples with microscopic light-matter interactions and propose that the suppression stems from photonic exchange. Our results demonstrate that cavity polariton formation can suppress disorder and show researchers how to design coherence into hybrid molecular material systems.

Observation of transition from superfluorescence to polariton condensation in CsPbBr3 quantum dots film

The superfluorescence effect has received extensive attention due to the many-body physics of quantum correlation in dipole gas and the optical applications of ultrafast bright radiation field based on the cooperative quantum state. Here, we demonstrate not only to observe the superfluorescence effect but also to control the cooperative state of the excitons ensemble by externally applying a regulatory dimension of coupling light fields. A new quasi-particle called cooperative exciton-polariton is revealed in a light-matter hybrid structure of a perovskite quantum dot thin film spin-coated on a Distributed Bragg Reflector. Above the nonlinear threshold, polaritonic condensation occurs at a nonzero momentum state on the lower polariton branch owning to the vital role of the synchronized excitons. The phase transition from superfluorescence to polariton condensation exhibits typical signatures of a decrease of the linewidth, an increase of the macroscopic coherence as well as an accelerated radiation decay rate. These findings are promising for opening new potential applications for super-brightness and unconventional coherent light sources and could enable the exploitation of cooperative effects for quantum optics.

Radiative pumping in a strongly coupled microcavity filled with a neat molecular film showing excimer emission.

Strong light-matter interactions have attracted much attention as a means to control the physical/chemical properties of organic semiconducting materials with light-matter hybrids called polaritons. To unveil the processes under strong coupling, studies on the dynamics of polaritons are of particular importance. While highly condensed molecular materials with large dipole density are ideal to achieve strong coupling, the emission properties of such films often become a mixture of monomeric and excimeric components, making the role of excimers unclear. Here, we use amorphous neat films of a new bis(phenylethynyl anthracene) derivative showing only excimer emission and investigate the excited-state dynamics of a series of strongly coupled microcavities, with each cavity being characterised by a different exciton-photon detuning. A time-resolved photoluminescence study shows that the excimer radiatively pumps the lower polariton in the relaxation process and the decay profile reflects the density of states. The delayed emission derived from triplet-triplet annihilation is not sensitive to the cavity environment, possibly due to the rapid excimer formation. Our results highlight the importance of controlling intermolecular interactions towards rational design of organic exciton-polariton devices, whose performance depends on efficient polariton relaxation pathways.

The role of IR inactive mode in W(CO)6 polariton relaxation process

Abstract Vibrational polaritons have shown potential in influencing chemical reactions, but the exact mechanism by which they impact vibrational energy redistribution, crucial for rational polariton chemistry design, remains unclear. In this work, we shed light on this aspect by revealing the role of solvent phonon modes in facilitating the energy relaxation process from the polaritons formed of a T 1u mode of W(CO)6 to an IR inactive E g mode. Ultrafast dynamic measurements indicate that along with the direct relaxation to the dark T 1u modes, lower polaritons also transition to an intermediate state, which then subsequently relaxes to the T 1u mode. We reason that the intermediate state could correspond to the near-in-energy Raman active E g mode, which is populated through a phonon scattering process. This proposed mechanism finds support in the observed dependence of the IR-inactive state’s population on the factors influencing phonon density of states, e.g., solvents. The significance of the Raman mode’s involvement emphasizes the importance of non-IR active modes in modifying chemical reactions and ultrafast molecular dynamics.

Solution-processed halide perovskite microcavity exciton-polariton light-emitting diodes working at room temperature

Exciton-polaritons offer the potential to achieve electrically pumped perovskite polariton lasers with much lower current thresholds than conventional photonic lasers. While optically pumped exciton-polaritons have been widely studied in halide perovskites, electrically-pumped polaritons remain limited. In this study, we demonstrate the use of a solution-processing strategy to develop halide perovskite polariton light-emitting diodes (LEDs) that operate at room temperature. The strong coupling of excitons and cavity photons is confirmed through the dispersion relation from angle-resolved reflectivity, with a Rabi splitting energy of 64 meV. Our devices exhibit angle-resolved electroluminescence following the low polariton branch and achieve external quantum efficiencies of 1.7%, 3.85%, and 3.7% for detunings of 1.1, −77, and −128 meV, respectively. We also explore devices with higher efficiency of 5.37% and a narrower spectral bandwidth of 6.5 nm through the optimization of a top emitting electrode. Our work demonstrates, to our knowledge, the first room-temperature perovskite polariton LED with a typical vertical geometry and represents a significant step towards realizing electrically pumped perovskite polariton lasers.