Tailoring Dispersion of Room-Temperature Exciton-Polaritons with Perovskite-Based Subwavelength Metasurfaces.

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.

Directing random lasing emission using cavity exciton-polaritons.

Random lasing is an intriguing phenomenon occurring in disordered structures with optical gain in which light scattering provides the necessary feedback for lasing action. Unlike conventional lasers, random lasing systems emit in all directions due to light scattering. While this property can be desired in some cases, directional emission remains required for most applications. In a vertical microcavity containing the hybrid perovskite CH3NH3PbBr3, we report here the coupling of the emission of a random laser with a cavity polaritonic resonance, resulting in a directional random lasing, whose emission angles can be tuned by varying the cavity detuning and reach values as large as 15.8° and 22.4°.

Using Low Temperature Photoluminescence Spectroscopy to Investigate CH3NH3PbI3 Hybrid Perovskite Degradation.

Investigating the stability and evaluating the quality of the CH3NH3PbI3 perovskite structures is quite critical both to the design and fabrication of high-performance perovskite devices and to fundamental studies of the photophysics of the excitons. In particular, it is known that, under ambient conditions, CH3NH3PbI3 degrades producing some PbI2. We show here that low temperature Photoluminescence (PL) spectroscopy is a powerful tool to detect PbI2 traces in hybrid perovskite layers and single crystals. Because PL spectroscopy is a signal detection method on a black background, small PbI2 traces can be detected, when other methods currently used at room temperature fail. Our study highlights the extremely high stability of the single crystals compared to the thin layers and defects and grain boundaries are thought to play an important role in the degradation mechanism.

Ionic Field Screening in MAPbBr3 Crystals Revealed from Remnant Sensitivity in X-ray Detection.

Research on metal halide perovskites as absorbers for X-ray detection is an attractive subject due to the optimal optoelectronic properties of these materials for high-sensitivity applications. However, the contact degradation and the long-term instability of the current limit the performance of the devices, in close causality with the dual electronic-ionic conductivity of these perovskites. Herein, millimeter-thick methylammonium-lead bromide (MAPbBr3) single and polycrystalline samples are approached by characterizing their long-term dark current and photocurrent under X-ray incidence. It is shown how both the dark current and the sensitivity of the detectors follow similar trends at short-circuit (V = 0 V) after biasing. By performing drift-diffusion numerical simulations, it is revealed how large ionic-related built-in fields not only produce relaxations to equilibrium lasting up to tens of hours but also continue to affect the charge kinetics under homogeneous low photogeneration rates. Furthermore, a method is suggested for estimating the ionic mobility and concentration by analyzing the initial current at short-circuit and the characteristic diffusion times.

X-Ray-Induced Modification of the Photophysical Properties of MAPbBr3 Single Crystals.

Methylammonium lead tribromide (MAPbBr3) perovskite single crystals demonstrate to be excellent direct X-ray and gamma-ray detectors with outstanding sensitivity and low limit of detection. Despite this, thorough studies on the photophysical effects of exposure to high doses of ionizing radiation on this material are still lacking. In this work, we present our findings regarding the effects of controlled X-ray irradiation on the optoelectronic properties of MAPbBr3 single crystals. Irradiation is carried out in air with an imaging X-ray tube, simulating real-life application in a medical facility. By means of surface photovoltage spectroscopy, we find that X-ray exposure quenches free excitons in the material and introduces new bound excitonic species. Despite this drastic effect, the crystals recover after 1 week of storage in dark and low humidity conditions. By means of X-ray photoelectron spectroscopy, we find that the origin of the new bound excitonic species is the formation of bromine vacancies, leading to local changes in the dielectric response of the material. The recovery effect is attributed to vacancy filling by atmospheric oxygen and water.

Tetrazine molecules as an efficient electronic diversion channel in 2D organic-inorganic perovskites.

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-Exciton Annihilation in Two-Dimensional Halide Perovskites at Room Temperature.

Recently, Ruddlesden-Popper 2D perovskite (RPP) solar cells and light-emitting diodes (LEDs) have shown promising efficiencies and improved stability in comparison to 3D halide perovskites. Here, the exciton recombination dynamics is investigated at room temperature in pure-phase RPP crystals (C6H5C2H4NH3)2(CH3NH3)n-1PbnI3n+1 (n = 1, 2, 3, and 4) by time-resolved photoluminescence (TRPL) in a large range of power excitations. As the number of perovskite layers increases, we detect the presence of an increasing fraction of out-of-equilibrium free carriers just after photoexcitation, on a picosecond time scale, while the dynamics is characterized by the recombination of excitons with long lifetime spanning several tens of nanoseconds. At low excitation power, the TRPL decays are nonexponential because of defect-assisted recombination. At high fluence, defects are filled and many-body interactions become important. Similar to other 2D systems, exciton-exciton annihilation (EEA) is then the dominant recombination path in a high-density regime below the Mott transition.

Impact of Reabsorption on the Emission Spectra and Recombination Dynamics of Hybrid Perovskite Single Crystals.

Understanding the surface properties of organic-inorganic lead-based perovskites is of high importance to improve the device's performance. Here, we have investigated the differences between surface and bulk optical properties of CH3NH3PbBr3 single crystals. Depth-resolved cathodoluminescence was used to probe the near-surface region on a depth of a few microns. In addition, we have studied the transmitted luminescence through thicknesses between 50 and 600 µm. In both experiments, the expected spectral shift due to the reabsorption effect has been precisely calculated. We demonstrate that reabsorption explains the important variations reported for the emission energy of single crystals. Single crystals are partially transparent to their own luminescence, and radiative transport is the dominant mechanism for propagation of the excitation in thick crystals. The transmitted luminescence dynamics are characterized by a long rise time and a lengthening of their decay due to photon recycling and light trapping.

Narrow Linewidth Excitonic Emission in Organic-Inorganic Lead Iodide Perovskite Single Crystals.

Hybrid perovskite thin films have demonstrated impressive performance for solar energy conversion and optoelectronic applications. However, further progress will benefit from a better knowledge of the intrinsic photophysics of materials. Here, the temperature-dependent emission properties of CH3NH3PbI3 single crystals are investigated and compared to those of thin polycrystalline films by means of steady-state and time-resolved photoluminescence spectroscopy. Single crystals photoluminescence present a sharp excitonic emission at high energy, with full width at half maximum of only 5 meV, assigned to free excitonic recombination. We highlight a strong thermal broadening of the free excitonic emission, due to exciton-LO-phonon coupling. The emission turned to be very short-lived with a subnanosecond dynamics, mainly induced by the fast trapping of the excitons. The free excitonic emission is completely absent of the thin film spectra, which are dominated by trap state bands.