Unveiling Charge-Transfer Dynamics at Singlet Fission Layer/Hybrid Perovskite Interface.

Singlet fission (SF) materials have been applied in various types of solar cells to pursue higher power conversion efficiency (PCE) beyond the Shockley-Queisser (SQ) limit. SF implementation in perovskite solar cells has not been successfully realized yet due to the insufficient understanding of the SF/perovskite heterojunctions. In this work, we attempt to elucidate the charge dynamics of an SF/perovskite system by incorporating a well-known SF molecule, TIPS-pentacene, and a triple-cation perovskite Cs0.05(FA0.85MA0.15)0.95PbI2.55Br0.45, owing to their well-matched energy structures. The transient absorption spectra and kinetic fitting plots suggest an electron-transfer process from the triplet state of TIPS-pentacene to perovskite in the picosecond regime, which increases the carrier density by 20% in the perovskite layer. This work confirms the existence of an electron-transfer process between the SF material and perovskite, providing a pathway to SF-enhanced perovskite solar cells.

Directional Emission from Electrically Injected Exciton-Polaritons in Perovskite Metasurfaces.

We present a new approach to achieving strong coupling between electrically injected excitons and photonic bound states in the continuum of a dielectric metasurface. Here a high-finesse metasurface cavity is monolithically patterned in the channel of a perovskite light-emitting transistor to induce a large Rabi splitting of ∼200 meV and more than 50-fold enhancement of the polaritonic emission compared to the intrinsic excitonic emission of the perovskite film. Moreover, the directionality of polaritonic electroluminescence can be dynamically tuned by varying the source-drain bias, which induces an asymmetric distribution of exciton population within the transistor channel. We argue that this approach provides a new platform to study strong light-matter interactions in dispersion engineered photonic cavities under electrical injection and paves the way to solution-processed electrically pumped polariton lasers.

Perovskite quantum dot one-dimensional topological laser.

Various topological laser concepts have recently enabled the demonstration of robust light-emitting devices that are immune to structural deformations and tolerant to fabrication imperfections. Current realizations of photonic cavities with topological boundaries are often limited by outcoupling issues or poor directionality and require complex design and fabrication that hinder operation at small wavelengths. Here we propose a topological cavity design based on interface states between two one-dimensional photonic crystals with distinct Zak phases. Using a few monolayers of solution-processed all-inorganic cesium lead halide perovskite quantum dots as the ultrathin gain medium, we demonstrate a lithography-free, vertical-emitting, low-threshold, and single-mode laser emitting in the green. We show that the topological laser, akin to vertical-cavity surface-emitting lasers (VCSELs), is robust against local perturbations of the multilayer structure. We argue that the design simplicity and reduction of the gain medium thickness enabled by the topological cavity make this architecture suitable for low-cost and efficient quantum dot vertical emitting lasers operating across the visible spectral region.

Topological Insulator Metamaterials.

Confinement of electromagnetic fields at the subwavelength scale via metamaterial paradigms is an established method to engineer light-matter interaction in most common material systems, from insulators to semiconductors and from metals to superconductors. In recent years, this approach has been extended to the realm of topological materials, providing a new avenue to access nontrivial features of their electronic band structure. In this review, we survey various topological material classes from a photonics standpoint, including crystal growth and lithographic structuring methods. We discuss how exotic electronic features such as spin-selective Dirac plasmon polaritons in topological insulators or hyperbolic plasmon polaritons in Weyl semimetals may give rise to unconventional magneto-optic, nonlinear, and circular photogalvanic effects in metamaterials across the visible to infrared spectrum. Finally, we dwell on how these effects may be dynamically controlled by applying external perturbations in the form of electric and magnetic fields or ultrafast optical pulses. Through these examples and future perspectives, we argue that topological insulator, semimetal and superconductor metamaterials are unique systems to bridge the missing links between nanophotonic, electronic, and spintronic technologies.

Phase-Change Perovskite Microlaser with Tunable Polarization Vortex.

Metasurfaces supporting optical bound states in the continuum (BICs) are emerging as simple and compact optical cavities to realize polarization-vortex lasers. The winding of the polarization around the singularity defines topological charges which are generally set by the cavity design and cannot be altered without changing geometrical parameters. Here, a subwavelength-thin phase-change halide perovskite BIC metasurface functioning as a tunable polarization vortex microlaser is demonstrated. Upon the perovskite structural phase transitions, both its refractive index and gain vary substantially, inducing reversible and bistable switching between distinct polarization vortexes underpinned by opposite topological charges. Dynamic tuning and switching of the resulting vector beams may find use in microscopy imaging, particle trapping and manipulation, and optical data storage.

Polarization-Tunable Perovskite Light-Emitting Metatransistor.

Emerging immersive visual communication technologies require light sources with complex functionality for dynamic control of polarization, directivity, wavefront, spectrum, and intensity of light. Currently, this is mostly achieved by free space bulk optic elements, limiting the adoption of these technologies. Flat optics based on artificially structured metasurfaces that operate at the sub-wavelength scale are a viable solution, however, their integration into electrically driven devices remains challenging. Here, a radically new approach to monolithic integration of a dielectric metasurface into a perovskite light-emitting transistor is demonstrated. It is shown that nanogratings directly structured on top of the transistor channel yield an 8-fold increase of electroluminescence intensity and dynamic tunability of polarization. This new light-emitting metatransistor device concept opens unlimited opportunities for light management strategies based on metasurface design and integration.

Resonant Enhancement of Polymer-Cell Optostimulation by a Plasmonic Metasurface.

Organic semiconductors have shown great potential as efficient bioelectronic materials. Specifically, photovoltaic polymers such as the workhorse poly(thiophene) derivatives, when stimulated with visible light, can depolarize neurons and generate action potentials, an effect that has been also employed for rescuing vision in blind rats. In this context, however, the coupling of such materials with optically resonant structures to enhance those photodriven biological effects is still in its infancy. Here, we employ the optical coupling between a nanostructured metasurface and poly(3-hexylthiophene) (P3HT) to improve the bioelectronic effects occurring upon photostimulation at the abiotic-biotic interface. In particular, we designed a spectrally tuned aluminum metasurface that can resonate with P3HT, hence augmenting the effective field experienced by the polymer. In turn, this leads to an 8-fold increase in invoked inward current in cells. This enhanced activation strategy could be useful to increase the effectiveness of P3HT-based prosthetic implants for degenerative retinal disorders.

Perovskite metasurfaces with large superstructural chirality.

Recent attempts to synthesize hybrid perovskites with large chirality have been hampered by large size mismatch and weak interaction between their structure and the wavelength of light. Here we adopt a planar nanostructure design to overcome these limitations and realize all-dielectric perovskite metasurfaces with giant superstructural chirality. We identify a direct spectral correspondence between the near- and the far- field chirality, and tune the electric and magnetic multipole moments of the resonant chiral metamolecules to obtain large anisotropy factor of 0.49 and circular dichroism of 6350 mdeg. Simulations show that larger area metasurfaces could yield even higher optical activity, approaching the theoretical limits. Our results clearly demonstrate the advantages of nanostructrure engineering for the implementation of perovskite chiral photonic, optoelectronic, and spintronic devices.

Optical Rashba Effect in a Light-Emitting Perovskite Metasurface.

The Rashba effect, i.e., the splitting of electronic spin-polarized bands in the momentum space of a crystal with broken inversion symmetry, has enabled the realization of spin-orbitronic devices, in which spins are manipulated by spin-orbit coupling. In optics, where the helicity of light polarization represents the spin degree of freedom for spin-momentum coupling, the optical Rashba effect is manifested by the splitting of optical states with opposite chirality in the momentum space. Previous realizations of the optical Rashba effect relied on passive devices determining the surface plasmon or light propagation inside nanostructures, or the directional emission of chiral luminescence when hybridized with light-emitting media. An active device underpinned by the optical Rashba effect is demonstrated here, in which a monolithic halide perovskite metasurface emits highly directional chiral photoluminescence. An all-dielectric metasurface design with broken in-plane inversion symmetry is directly embossed into the high-refractive-index, light-emitting perovskite film, yielding a degree of circular polarization of photoluminescence of 60% at room temperature.

Picosecond Charge Localization Dynamics in CH3NH3PbI3 Perovskite Probed by Infrared-Activated Vibrations.

Hybrid metal halide perovskites exhibit well-defined semiconducting properties and efficient optoelectronic performance considering their soft crystal structure and low-energy lattice motions. The response of such a crystal lattice to light-induced charges is a fundamental question, for which experimental insight into ultrafast time scales is still sought. Here, we use infrared-activated vibrations (IRAV) of the organic components within the hybrid perovskite lattice as a sensitive probe for local structural reorganizations after photoexcitation, with femtosecond resolution. We find that the IRAV signal response shows a delayed rise of about 3 ps and subsequent decay of pronounced monomolecular character, distinguishing it from absorption associated with free carriers. We interpret our results as a two-step carrier localization process. Initially, carriers localize transiently in local energy minima formed by lattice fluctuations. A subpopulation of these can then fall into deeper trapped states over picoseconds, likely due to local reorganization of the organic molecules surrounding the carriers.

Symmetry perception with spiking neural networks.

Mirror symmetry is an abundant feature in both nature and technology. Its successful detection is critical for perception procedures based on visual stimuli and requires organizational processes. Neuromorphic computing, utilizing brain-mimicked networks, could be a technology-solution providing such perceptual organization functionality, and furthermore has made tremendous advances in computing efficiency by applying a spiking model of information. Spiking models inherently maximize efficiency in noisy environments by placing the energy of the signal in a minimal time. However, many neuromorphic computing models ignore time delay between nodes, choosing instead to approximate connections between neurons as instantaneous weighting. With this assumption, many complex time interactions of spiking neurons are lost. Here, we show that the coincidence detection property of a spiking-based feed-forward neural network enables mirror symmetry. Testing this algorithm exemplary on geospatial satellite image data sets reveals how symmetry density enables automated recognition of man-made structures over vegetation. We further demonstrate that the addition of noise improves feature detectability of an image through coincidence point generation. The ability to obtain mirror symmetry from spiking neural networks can be a powerful tool for applications in image-based rendering, computer graphics, robotics, photo interpretation, image retrieval, video analysis and annotation, multi-media and may help accelerating the brain-machine interconnection. More importantly it enables a technology pathway in bridging the gap between the low-level incoming sensor stimuli and high-level interpretation of these inputs as recognized objects and scenes in the world.

Image reconstruction through a multimode fiber with a simple neural network architecture.

Multimode fibers (MMFs) have the potential to carry complex images for endoscopy and related applications, but decoding the complex speckle patterns produced by mode-mixing and modal dispersion in MMFs is a serious challenge. Several groups have recently shown that convolutional neural networks (CNNs) can be trained to perform high-fidelity MMF image reconstruction. We find that a considerably simpler neural network architecture, the single hidden layer dense neural network, performs at least as well as previously-used CNNs in terms of image reconstruction fidelity, and is superior in terms of training time and computing resources required. The trained networks can accurately reconstruct MMF images collected over a week after the cessation of the training set, with the dense network performing as well as the CNN over the entire period.

Metamaterial Enhancement of Metal-Halide Perovskite Luminescence.

Metal-halide perovskites are rapidly emerging as solution-processable optical materials for light-emitting applications. Here, we adopt a plasmonic metamaterial approach to enhance photoluminescence emission and extraction of methylammonium lead iodide (MAPbI3) thin films based on the Purcell effect. We show that hybridization of the active metal-halide film with resonant nanoscale sized slits carved into a gold film can yield more than 1 order of magnitude enhancement of luminescence intensity and nearly 3-fold reduction of luminescence lifetime corresponding to a Purcell enhancement factor of more than 300. These results show the effectiveness of resonant nanostructures in controlling metal-halide perovskite light emission properties over a tunable spectral range, a viable approach toward highly efficient perovskite light-emitting devices and single-photon emitters.

Exciton-Enabled Meta-Optics in Two-Dimensional Transition Metal Dichalcogenides.

Optical wavefront engineering has been rapidly developing in fundamentals from phase accumulation in the optical path to the electromagnetic resonances of confined nanomodes in optical metasurfaces. However, the amplitude modulation of light has limited approaches that usually originate from the ohmic loss and absorptive dissipation of materials. Here, an atomically thin photon-sieve platform made of MoS2 multilayers is demonstrated for high-quality optical nanodevices, assisted fundamentally by strong excitonic resonances at the band-nesting region of MoS2. The atomic thin MoS2 significantly facilitates high transmission of the sieved photons and high-fidelity nanofabrication. A proof-of-concept two-dimensional (2D) nanosieve hologram exhibits 10-fold enhanced efficiency compared with its non-2D counterparts. Furthermore, a supercritical 2D lens with its focal spot breaking diffraction limit is developed to exhibit experimentally far-field label-free aberrationless imaging with a resolution of ∼0.44λ at λ = 450 nm in air. This transition-metal-dichalcogenide (TMDC) photonic platform opens new opportunities toward future 2D meta-optics and nanophotonics.

Black GaAs: Gold-Assisted Chemical Etching for Light Trapping and Photon Recycling.

Thanks to its excellent semiconductor properties, like high charge carrier mobility and absorption coefficient in the near infrared spectral region, GaAs is the material of choice for thin film photovoltaic devices. Because of its high reflectivity, surface microstructuring is a viable approach to further enhance photon absorption of GaAs and improve photovoltaic performance. To this end, metal-assisted chemical etching represents a simple, low-cost, and easy to scale-up microstructuring method, particularly when compared to dry etching methods. In this work, we show that the etched GaAs (black GaAs) has exceptional light trapping properties inducing a 120 times lower surface reflectance than that of polished GaAs and that the structured surface favors photon recycling. As a proof of principle, we investigate photon reabsorption in hybrid GaAs:poly (3-hexylthiophene) heterointerfaces.

Phase stabilization of a coherent fiber network by single-photon counting.

Coherent optical fiber networks are extremely sensitive to thermal, mechanical, and acoustic noise, which requires elaborate schemes of phase stabilization with dedicated auxiliary lasers, multiplexers, and photodetectors. This is particularly demanding in quantum networks operating at the single-photon level. Here, we propose a simple method of phase stabilization based on single-photon counting and apply it to quantum fiber networks implementing single-photon interference on a lossless beamsplitter and coherent perfect absorption on a metamaterial absorber. As a proof of principle, we show dissipative single-photon switching with visibility close to 80%. This method can be employed in quantum networks of greater complexity without classical stabilization rigs, potentially increasing efficiency of the quantum channels.

Publisher Correction: Mixed-Dimensional Naphthylmethylammonium-Methylammonium Lead Iodide Perovskites with Improved Thermal Stability.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Mixed-Dimensional Naphthylmethylammoinium-Methylammonium Lead Iodide Perovskites with Improved Thermal Stability.

Metal halide perovskite solar cells, despite achieving high power conversion efficiency (PCE), need to demonstrate high stability prior to be considered for industrialization. Prolonged exposure to heat, light, and moisture is known to deteriorate the perovskite material owing to the breakdown of the crystal structure into its non-photoactive components. In this study, we show that by combining the organic ligand 1-naphthylmethylammoinium iodide (NMAI) with methylammonium (MA) to form a mixed dimensional (NMA)2(MA)n-1PbnI3n+1 perovskite the optical, crystallographic and morphological properties of the newly formed mixed dimensional perovskite films under thermal ageing can be retained. Indeed, under thermal ageing at 85 °C, the best performing (NMA)2(MA)n-1PbnI3n+1 perovskites films show a stable morphology, a low PbI2 formation rate and a significantly reduced variation of both MA-specific vibrational modes and fluorescence lifetimes as compared to the pristine MAPbI3 films. These results highlight the role of the bulky NMA+ organic cation in mixed dimensional perovskites to both inhibit the MA+ diffusion and reduce the material defects, which act as non-radiative recombination centres. As a result, the thermal stability of metal halide perovskites has been substantially improved.

All-polymer methylammonium lead iodide perovskite microcavities.

Thanks to a high photoluminescence quantum yield, large charge carrier diffusion, and ease of processing from solution, perovskite materials are becoming increasingly interesting for flexible optoelectronic devices. However, their deposition requires wide range solvents that are incompatible with many other flexible and solution-processable materials, including polymers. Here, we show that methylammonium lead iodide (MAPbI3) films can be directly synthesized on all-polymer microcavities via simple addition of a perfluorinated layer which protects the polymer photonic structure from the perovskite processing solvents. The new processing provides microcavities with a quality factor Q = 155, that is in agreement with calculations and the largest value reported so far for fully solution processed perovskite microcavities. Furthermore, the obtained microcavity shows strong spectral and angular redistribution of the the MAPbI3 photoluminescence spectrum, which shows a 3.5 fold enhanced intensity with respect to the detuned reference. The opportunity to control and modify the emission of a MAPbI3 film via a simple spun-cast polymer structure is of great interest in advanced optoelectronic applications requiring high colour purity or emission directionality.

The Photophysics of Polythiophene Nanoparticles for Biological Applications.

In this work the photophysics of poly(3-hexylthiophene) nanoparticles (NPs) is investigated in the context of their biological applications. The NPs, made as colloidal suspensions in aqueous buffers, present a distinct absorption band in the low-energy region. On the basis of systematic analysis of absorption and transient absorption (TA) spectra taken under different pH conditions, this band is associated with charge-transfer states generated by the polarization of loosely bound polymer chains and originating from complexes formed with electron-withdrawing species. Importantly, the ground-state depletion of these states upon photoexcitation is active even on microsecond timescales, thus suggesting that they act as precursor states for long-living polarons; this could be beneficial for cellular stimulation. Preliminary transient absorption microscopy results for NPs internalized within the cells reveal the presence of long-living species, further substantiating their relevance in biointerfaces.