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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.

Friedrich–Wintgen (FW) interference is an atypical coupling mechanism that grants loss exchange between leaky resonances in non-Hermitian classical and quantum systems. Intriguingly, such a mechanism makes destructive interference possible for scenarios in which a radiating wave becomes a bound state in the continuum (BIC) by giving away all of its losses. Here we propose and demonstrate experimentally an original concept to tailor FW-BICs with polarization singularity at on-demand wavevectors in an optical metasurface. As a proof-of-concept, using hybrid organic–inorganic halide perovskite as an active material, we empower this novel polarization singularity to obtain lasing emission, exhibiting both highly directional emission at oblique angles and a polarization vortex in momentum space. Our results pave the way to steerable coherent emission with a tailored polarization pattern for applications in optical communication/manipulation in free space, high-resolution imaging/focusing, and data storage.

The large tolerance of hybrid perovksites to the trapping of electrons by defects is a key asset in photovoltaic applications. Here, the ionic surface terminations of CH3NH3PbI3are employed as a testbed to study the effect of electrostatic fields on the dynamics of excited carriers. We characterize the transition across the tetragonal to orthorhombic phase. The observed type II band offset and drift of the excited electrons highlight the important role that organic cations have on the screening of local electrostatic fields. When the orientation of organic cations is frozen in the orthorhombic phase, the positively charged termination induces a massive accumulation of excited electrons at the surface of the sample. Conversely, no electron accumulation is observed in the tetragonal phase. We conclude that the local fields cannot penetrate in the sample when the polarizability of freely moving cations boosts the dielectric constant up to ε = 120.

Lead-halide perovskites are generally excellent light emitters and can have larger exciton binding energies than thermal energy at room temperature, exhibiting great promise for room-temperature exciton-polaritonics. Rapid progress has been made recently, although challenges and mysteries remain in lead-halide perovskite semiconductors to push polaritons to room-temperature operation. In this Perspective, we discuss fundamental aspects of perovskite semiconductors for exciton-polaritons and review the recent rapid experimental advances using lead-halide perovskites for room-temperature polaritonics, including the experimental realization of strong light–matter interaction using various types of microcavities as well as reaching the polariton condensation regime in planar microcavities and lattices.

Taking advantage of an innovative design concept for layered halide perovskites with active chromophores acting as organic spacers, we present here the synthesis of two novel two-dimensional (2D) hybrid organic–inorganic halide perovskites incorporating for the first time 100% of a photoactive tetrazine derivative as the organic component. Namely, the use of a heterocyclic ring containing a nitrogen proportion imparts a unique electronic structure to the organic component, with the lowest energy optical absorption in the blue region. The present compound, a tetrazine, presents several resonances between the organic and inorganic components, both in terms of single particle electronic levels and exciton states, providing the ideal playground to discuss charge and energy transfer mechanisms at the organic/inorganic interface. Photophysical studies along with hybrid time-dependent DFT simulations demonstrate partial energy transfer and rationalise the suppressed emission from the perovskite frame in terms of different energy-transfer diversion channels, potentially involving both singlet and triplet states of the organic spacer. Periodic DFT simulations also support the feasibility of electron transfer from the conduction band of the inorganic component to the LUMO of the spacer as a potential quenching mechanism, suggesting the coexistence and competition of charge and energy transfer mechanisms in these heterostructures. Our work proves the feasibility of inserting photoactive small rings in a 2D perovskite structure, meanwhile providing a robust frame to rationalize the electronic interactions between the semiconducting inorganic layer and organic chromophores, with the prospects of optimizing the organic moiety according to the envisaged application.

Exciton-polaritons represent a promising platform for studying quantum fluids of light and realizing prospective all-optical devices. Here we report on the experimental demonstration of exciton-polaritons at room temperature in resonant metasurfaces made from a sub-wavelength two-dimensional lattice of perovskite pillars. The strong coupling regime is revealed by both angular-resolved reflectivity and photoluminescence measurements, showing anticrossing between photonic modes and the exciton resonance with a Rabi splitting in the 200 meV range. Moreover, by tailoring the photonic Bloch mode to which perovskite excitons are coupled, polaritonic dispersions are engineered exhibiting linear, parabolic, and multivalley dispersions. All of our results are perfectly reproduced by both numerical simulations based on a rigorous coupled wave analysis and an elementary model based on a quantum theory of radiation–matter interaction. Our results suggest a new approach to study exciton-polaritons and pave the way toward large-scale and low-cost integrated polaritonic devices operating at room temperature.

Véritables stars des conférences d’optoélectronique depuis déjà 5 ans, les pérovskites hybrides apparaissent comme une nouvelle classe de semiconducteurs qui montrent des performances exceptionnelles, donnant l’espoir de produire des dispositifs photoniques efficaces à faible coût et flexibles. Le matériau ayant émergé il y a peu, ses déclinaisons chimiques, sa qualité cristalline et ses propriétés photophysiques représentent un grand champ d’investigation pour les physiciens et les chimistes.

In this review we examine recent theoretical investigations on 2D and 3D hybrid perovskites (HOPs) that combine classical solid-state physics concepts and density functional theory (DFT) simulations as a tool for studying their optoelectronic properties. Such an approach allows one to define a new class of semiconductors, where the pseudocubic high-temperature perovskite structure plays a central role. Bloch states and k.p. Hamiltonians yield new insight into the influence of lattice distortions, including loss of inversion symmetry, as well as spin–orbit coupling. Electronic band folding and degeneracy, effective masses, and optical absorption are analyzed. Concepts of Bloch and envelope functions, as well as confinement potential, are discussed in the context of layered HOP and 3D HOP heterostructures. Screening and dielectric confinements are important for room-temperature optical properties of 3D and layered HOP, respectively. Nonradiative Auger effects are analyzed for the first time close to the electronic band gap of 3D hybrid perovskites.

A great advantage of the hybrid organic–inorganic perovskites is the chemical flexibility and the possibility of a molecular engineering of each part of the material (the inorganic part and the organic part respectively) in order to improve or add some functionalities. An adequately chosen organic luminophore has been introduced inside a lead bromide type organic–inorganic perovskite, while respecting the two-dimensional perovskite structure. A substantial increase of the brilliance of the perovskite is obtained. This activation of the perovskite luminescence by the adequate engineering of the organic part is an original approach, and is particularly interesting in the framework of the light-emitting devices such as organic light-emitting diodes (OLEDs) or lasers.

Energy transfer in noncovalently bound porphyrin/carbon nanotube compounds is investigated at the single-nanocompound scale. Excitation spectroscopy of the luminescence of the nanotube shows two resonances arising from intrinsic excitation of the nanotube and from energy transfer from the porphyrin. Polarization diagrams show that both resonances are highly anisotropic, with a preferred direction along the tube axis. The energy transfer is thus strongly anisotropic despite the almost isotropic absorption of porphyrins. We account for this result by local field effects induced by the large optical polarizability of nanotubes. We show that the local field correction extends over several nanometers outside the nanotubes and drives the overall optical response of functionalized nanotubes.

Single-wall carbon nanotubes noncovalently functionalized with porphyrin molecules have proven to be a very promising light harvesting system either for energy or charge transfer. In this work, we investigate the dynamics of this coupling at a subpicosecond time-scale, by means of transient absorption spectroscopy. We show that the ground state recovery time of the porphyrin is reduced by several orders of magnitude in the compound compared to the case of pristine porphyrin. Concomitantly, a strong bleaching signal is observed on the optical resonances of the nanotubes showing an ultrafast population buildup upon excitation of the porphyrin. We conclude that the energy transfer occurs on a time-scale shorter than 100 fs. Two-color measurements show that higher excited states of the nanotubes are populated on the same time-scale raising the point of the transfer mechanism. We briefly discuss two possible mechanisms.

The formation of a two-dimensional (2D) three-dimensional (3D) perovskite heterostructure has lately proved to be a promising way to improve the interface between the perovskite and electron/hole transport layers in perovskite solar cells, which is crucial for better device efficiency and stability. Herein, a spacer cation, 4-fluorophenethylammonium iodide, in isopropyl alcohol was used to form a thin 2D perovskite layer on top of a 3D triple-cation perovskite by a spin-coating deposition process. Therefore, a significant improvement in the device open-circuit voltage is obtained, leading to an enhanced power conversion efficiency. The formation mechanism of the 2D perovskite layer was studied by analyzing the structural, chemical, and optoelectronic properties of the layer, while varying several synthesis parameters. We reveal the presence of bromide inside the 2D phase and conclude with the existence of a concomitant formation mechanism, besides the most commonly described one involving the lead iodide (PbI2) excess contained in the 3D bulk. Therefore, we demonstrate how the stoichiometry of the 2D perovskite is affected by the chemical composition of the 3D layer underneath. This work provides new insights into the synthesis mechanisms of 2D/3D perovskite heterostructures, which could help to optimize their fabrication processes and develop new efficient and functional 2D/3D structures.

We report on the fabrication of a perovskite-based ((C_6H_5C_2H_4−NH_3)_2PbI_4) planar microcavity with a technique of a top dielectric mirror’s migration in liquid, avoiding the degradation of the perovskite material. This approach allows for increasing the cavity Q-factor, without degrading the fragile molecular material. Strong coupling of the perovskite exciton to both the cavity mode and the first Bragg mode is evidenced from angle-resolved reflectivity and microphotoluminescence measurements at room temperature; an efficient relaxation toward the minimum of the main polariton branch is observed. The measured quality factor is significantly increased compared to previous reports where a top metallic mirror was used, showing the decisive advantage of the present fabrication technique toward the achievement of stimulated effects and polariton lasing with perovskite materials.

We propose a migration technique for the deposition of the top dielectric mirror in the fabrication of planar microcavities containing a fragile molecular active layer. Our goal is to preserve the active material during this deposition step. The technique is validated by the fabrication of a passive cavity, showing a quality factor similar to that achieved by a conventional monolithic approach. The migration technique is then used to fabricate a perovskite-based organic-inorganic microcavity for emission in the strong coupling regime. Polariton emission lines are well resolved at room temperature, and efficient polariton relaxation toward the lowest energy polariton states is achieved using the migration method.

We propose a migration technique for the deposition of the top dielectric mirror in the fabrication of planar microcavities containing a fragile molecular active layer. Our goal is to preserve the active material during this deposition step. The technique is validated by the fabrication of a passive cavity, showing a quality factor similar to that achieved by a conventional monolithic approach. The migration technique is then used to fabricate a perovskite-based organic-inorganic microcavity for emission in the strong coupling regime. Polariton emission lines are well resolved at room temperature, and efficient polariton relaxation toward the lowest energy polariton states is achieved using the migration method.