Strong Light-Matter Coupling in Lead Halide Perovskite Quantum Dot Solids.

Strong coupling between lead halide perovskite materials and optical resonators enables both polaritonic control of the photophysical properties of these emerging semiconductors and the observation of fundamental physical phenomena. However, the difficulty in achieving optical-quality perovskite quantum dot (PQD) films showing well-defined excitonic transitions has prevented the study of strong light-matter coupling in these materials, central to the field of optoelectronics. Herein we demonstrate the formation at room temperature of multiple cavity exciton-polaritons in metallic resonators embedding highly transparent Cesium Lead Bromide quantum dot (CsPbBr3-QD) solids, revealed by a significant reconfiguration of the absorption and emission properties of the system. Our results indicate that the effects of biexciton interaction or large polaron formation, frequently invoked to explain the properties of PQDs, are seemingly absent or compensated by other more conspicuous effects in the CsPbBr3-QD optical cavity. We observe that strong coupling enables a significant reduction of the photoemission line width, as well as the ultrafast modulation of the optical absorption, controllable by means of the excitation fluence. We find that the interplay of the polariton states with the large dark state reservoir plays a decisive role in determining the dynamics of the emission and transient absorption properties of the hybridized light-quantum dot solid system. Our results should serve as the basis for future investigations of PQD solids as polaritonic materials.

Effect of Connectivity on the Carrier Transport and Recombination Dynamics of Perovskite Quantum-Dot Networks.

Quantum-dot (QD) solids are being widely exploited as a solution-processable technology to develop photovoltaic, light-emission, and photodetection devices. Charge transport in these materials is the result of a compromise between confinement at the individual QD level and electronic coupling among the different nanocrystals in the ensemble. While this is commonly achieved by ligand engineering in colloidal-based systems, ligand-free QD assemblies have recently emerged as an exciting alternative where nanostructures can be directly grown into porous matrices with optical quality as well as control over their connectivity and, hence, charge transport properties. In this context, we present a complete photophysical study comprising fluence- and temperature-dependent time-resolved spectroscopy to study carrier dynamics in ligand-free QD networks with gradually varying degrees of interconnectivity, which we achieve by changing the average distance between the QDs. Analysis of the photoluminescence and absorption properties of the QD assemblies, involving both static and time-resolved measurements, allows us to identify the weight of the different recombination mechanisms, both radiative and nonradiative, as a function of QD connectivity. We propose a picture where carrier diffusion, which is needed for any optoelectronic application and implies interparticle transport, gives rise to the exposure of carriers to a larger defect landscape than in the case of isolated QDs. The use of a broad range of fluences permits extracting valuable information for applications demanding either low- or high-carrier-injection levels and highlighting the relevance of a judicious design to balance recombination and diffusion.

Enhancement of upconversion photoluminescence in phosphor nanoparticle thin films using metallic nanoantennas fabricated by colloidal lithography.

Lanthanide-doped upconversion nanoparticles (UCNPs), as multifunctional light sources, are finding utility in diverse applications ranging from biotechnology to light harvesting. However, the main challenge in realizing their full potential lies in achieving bright and efficient photon upconversion (UC). In this study, we present a novel approach to fabricate an array of gold nanoantennas arranged in a hexagonal lattice using a simple and inexpensive colloidal lithography technique, and demonstrate a significant enhancement of UC photoluminescence (UCPL) by up to 35-fold through plasmon-enhanced photoexcitation and emission. To elucidate the underlying physical mechanisms responsible for the observed UCPL enhancement, we provide a comprehensive theoretical and experimental characterization, including a detailed photophysical description and numerical simulations of the spatial electric field distribution. Our results shed light on the fundamental principles governing the enhanced UCNPs and pave the way for their potential applications in photonic devices.

Effect of the effective refractive index on the radiative decay rate in nanoparticle thin films.

In this work, we theoretically and experimentally study the influence of the optical environment on the radiative decay rate of rare-earth transitions in luminescent nanoparticles forming a thin film. We use electric dipole sources in finite-difference time-domain simulations to analyze the effect of modifying the effective refractive index of transparent layers made of phosphor nanocrystals doped with rare earth cations, and propose a correction to previously reported analytical models for calculating the radiative decay rate. Our predictions are tested against an experimental realization of such luminescent films, in which we manage to vary the effective refractive index in a gradual and controllable manner. Our model accurately accounts for the measurements attained, allows us to discriminate the radiative and non-radiative contributions to the time-resolved photoluminescence, and provides a way to rationally tune the spontaneous decay rate and hence the photoluminescence quantum yield in an ensemble of luminescent nanoparticles.

Ultrapure Green High Photoluminescence Quantum Yield from FAPbBr3 Nanocrystals Embedded in Transparent Porous Films.

Achieving highly transparent and emissive films based on perovskite quantum dots (PQDs) is a challenging task since their photoluminescence quantum yield (PLQY) typically drops abruptly when they are used as building blocks to make a solid. In this work, we obtain highly transparent films containing FAPbBr3 quantum dots that display a narrow green emission (λ = 530 nm, full width at half-maximum (FWHM) = 23 nm) with a PLQY as high as 86%. The method employed makes use of porous matrices that act as arrays of nanoreactors to synthesize the targeted quantum dots within their void space, providing both a means to keep them dispersed and a protective environment. Further infiltration with poly(methyl methacrylate) (PMMA) increases the mechanical and chemical stability of the ensemble and serves to passivate surface defects, boosting the emission of the embedded PQD and significantly reducing the width of the emission peak, which fulfills the requirements established by the Commission Internationale de l'Éclairage (CIE) to be considered an ultrapure green emitter. The versatility of this approach is demonstrated by fabricating a color-converting layer that can be easily transferred onto a light-emitting device surface to modify the spectral properties of the outgoing radiation.

Collective plasmonic resonances enhance the photoluminescence of rare-earth nanocrystal films processed by ultrafast annealing.

Herein, we demonstrate that rapid thermal annealing allows achieving close-to-one photoluminescence quantum yield while preserving the transparency of rare-earth nanocrystal films, which further enables their integration with nanophotonics. The combination with periodic arrays of aluminum nanodisks that support collective plasmonic resonances leads to enhanced directional emission.

Responsive Optical Materials Based on Ligand-Free Perovskite Quantum Dots Embedded in Mesoporous Scaffolds.

Herein we show that dispersing inorganic cesium lead bromide (CsPbBr3) perovskite quantum dots (QDs) in optical quality films, possessing an accessible and controlled pore size distribution, gives rise to fluorescent materials with a controlled and highly sensitive response to ambient changes. A scaffold-based synthesis approach is employed to obtain ligand-free QDs, whose pristine surface endows them with high sensitivity to the presence of different vapors in their vicinity. At the same time, the void network of the host offers a means to gradually expose the embedded QDs to such vapors. Under these conditions, the luminescent response of the QDs is mediated by the mesostructure of the matrix, which determines the rate at which vapor molecules will adsorb onto the pore walls and, eventually, condensate, filling the void space. With luminescence quantum yields as high as 60%, scaffold-supported ligand-free perovskite nanocrystals display intense photoemission signals over the whole process, as well as high photo- and chemical stability, which allows illuminating them for long periods of time and recovering the original response upon desorption of the condensed phase. The results herein presented open a new route to explore the application of perovskite QD-based materials in sensing.

Determination of the optical constants of ligand-free organic lead halide perovskite quantum dots.

Precise knowledge of the optical constants of perovskite lead halide quantum dots (QDs) is required to both understand their interaction with light and to rationally design and optimize the devices based on them. However, their determination from colloidal nanocrystal suspensions, or films made out of them, remains elusive, as a result of the difficulty in disentangling the optical constants of the organic capping ligands and those of the semiconductor itself. In this work, we extract the refractive index and extinction coefficient of ligand-free methylammonium lead iodide (MAPbI3) and bromide (MAPbBr3) nanocrystals. In order to prevent the use of organic ligands in the preparation, we follow a scaffold assisted synthetic procedure, which yields a composite film of high optical quality that can be independently and precisely characterized and modelled. In this way, the contribution of the guest nanocrystals can be successfully discriminated from that of the host matrix. Using a Kramers-Kronig consistent dispersion model along with an effective medium approximation, it is possible to derive the optical constants of the QDs by fitting the spectral dependence of light transmitted and reflected at different angles and polarizations. Our results indicate a strong dependence of the optical constants on the QD size. Small nanocrystals show remarkably large values of the extinction coefficient compared to their bulk counterparts. This analysis opens the door to the rigorous modelling of solar cells and light-emitting diodes with active layers based on perovskite QDs.

Nanoantennas Patterned by Colloidal Lithography for Enhanced Nanophosphor Light Emission.

Transparent coatings made of rare-earth doped nanocrystals, also known as nanophosphors, feature efficient photoluminescence and excellent thermal and optical stability. Herein, we demonstrate that the optical antennas prepared by colloidal lithography render thin nanophosphor films with a brighter emission. In particular, we fabricate gold nanostructures in the proximity of GdVO4:Eu3+ nanophosphors by metal evaporation using a mask made of a monolayer of polymer beads arranged in a triangular lattice. Optical modes supported by the antennas can be controlled by tuning the diameter of the polymer spheres in the colloidal mask, which determines the shape of the gold nanostructure, as confirmed by numerical simulations. Confocal microscopy reveals that metallic antennas induce brighter photoluminescence at specific spatial regions of the nanophosphor film at targeted frequencies as a result of the coupling between gold nanostructures and nanophosphors. Patterning of nanophosphor thin layers with arrays of metallic antennas offers an inexpensive nanophotonic solution to develop bright emitting coatings of interest for color conversion, labeling, or anti-counterfeiting.

Enhanced up-conversion photoluminescence in fluoride-oxyfluoride nanophosphor films by embedding gold nanoparticles.

Owing to their unique non-linear optical character, lanthanide-based up-converting materials are potentially interesting for a wide variety of fields ranging from biomedicine to light harvesting. However, their poor luminescent efficiency challenges the development of technological applications. In this context, localized surface plasmon resonances (LSPRs) have been demonstrated as a valuable strategy to improve light conversion. Herein, we utilize LSPR induced by gold nanoparticles (NPs) to enhance up-conversion photoluminescence (UCPL) in transparent, i.e. scattering-free, films made of nanophosphors formed by fluoride-oxyfluoride host matrix that feature high thermal stability. Transparency allows excitation by an external source without extinction losses caused by unwanted diffuse reflection. We provide a simple method to embed gold NPs in films made of YF/YOF:Yb3+,Er3+ UC nanophosphors, via preparation of a viscous paste composed of both UC nanophosphors and colloidal gold NPs, reducing complexity in sample fabrication. The dimensions of gold NPs are such that their associated LSPR matches spectrally with the green emission band of the Er3+ doped nanophosphors. In order to demonstrate the benefits of plasmonic nanoparticles for UCPL in nanophosphor films, we provide a careful analysis of the structural properties of the composite thin films along with precise characterization of the impact of the gold NPs on the photophysical properties of UC nanophosphors.

Effect of Spatial Inhomogeneity on Quantum Trapping.

An object that is immersed in a fluid and approaching a substrate may find a potential energy minimum at a certain distance due to the balance between attractive and repulsive Casimir-Lifshitz forces, a phenomenon referred to as quantum trapping. This equilibrium depends on the relative values of the dielectric functions of the materials involved. Herein, we study quantum trapping effects in planar nanocomposite materials and demonstrate that they are strongly dependent on the characteristics of the spatial inhomogeneity. As a model case, we consider spherical particles embedded in an otherwise homogeneous material. We propose an effective medium approximation that accounts for the effect of inclusions and find that an unprecedented and counterintuitive intense repulsive Casimir-Lifshitz force arises as a result of the strong optical scattering and absorption size-dependent resonances caused by their presence. Our results imply that the proper analysis of quantum trapping effects requires comprehensive knowledge and a detailed description of the potential inhomogeneity (caused by imperfections, pores, inclusions, and density variations) present in the materials involved.

Ultrastrong Exciton-Photon Coupling in Broadband Solar Absorbers.

The recent development of organic polaritonic solar cells, in which sunlight absorbers and photon modes of a resonator are hybridized as a result of their strong coupling, has revealed the potential this interaction offers to control and enhance the performance of these devices. In this approach, the photovoltaic cell is built in such a way that it also behaves as an optical cavity supporting spectrally well-defined resonances, which match the broad absorption bands of the dyes employed. Herein we focus on the experimental and theoretical analysis of the specific spectral and angular optical absorption characteristics of a broadband light harvester, namely a subphthalocyanine, when operating in the ultrastrong coupling regime. We discuss the implications of having a broad distribution of oscillator strengths and demonstrate that rational design of the layered structure is needed to optimize both the spectral and the angular response of the sunlight harvester dye.

Highly Versatile Upconverting Oxyfluoride-Based Nanophosphor Films.

Fluoride-based compounds doped with rare-earth cations are the preferred choice of materials to achieve efficient upconversion, of interest for a plethora of applications ranging from bioimaging to energy harvesting. Herein, we demonstrate a simple route to fabricate bright upconverting films that are transparent, self-standing, flexible, and emit different colors. Starting from the solvothermal synthesis of uniform and colloidally stable yttrium fluoride nanoparticles doped with Yb3+ and Er3+, Ho3+, or Tm3+, we find the experimental conditions to process the nanophosphors as optical quality films of controlled thickness between few hundreds of nanometers and several micrometers. A thorough analysis of both structural and photophysical properties of films annealed at different temperatures reveals a tradeoff between the oxidation of the matrix, which transitions through an oxyfluoride crystal phase, and the efficiency of the upconversion photoluminescence process. It represents a significant step forward in the understanding of the fundamental properties of upconverting materials and can be leveraged for the optimization of upconversion systems in general. We prove bright multicolor upconversion photoluminescence in oxyfluoride-based phosphor transparent films upon excitation with a 980 nm laser for both rigid and flexible versions of the layers, being possible to use the latter to coat surfaces of arbitrary shape. Our results pave the way toward the development of upconverting coatings that can be conveniently integrated in applications that demand a large degree of versatility.

Disentangling Electron-Phonon Coupling and Thermal Expansion Effects in the Band Gap Renormalization of Perovskite Nanocrystals.

The complex electron-phonon interaction occurring in bulk lead halide perovskites gives rise to anomalous temperature dependences, like the widening of the electronic band gap as temperature increases. However, possible confinement effects on the electron-phonon coupling in the nanocrystalline version of these materials remain unexplored. Herein, we study the temperature (ranging from 80 K to ambient) and hydrostatic pressure (from atmospheric to 0.6 GPa) dependence of the photoluminescence of ligand-free methylammonium lead triiodide nanocrystals with controlled sizes embedded in a porous silica matrix. This analysis allowed us to disentangle the effects of thermal expansion and electron-phonon interaction. As the crystallite size decreases, the electron-phonon contribution to the gap renormalization gains in importance. We provide a plausible explanation for this observation in terms of quantum confinement effects, showing that neither thermal expansion nor electron-phonon coupling effects may be disregarded when analyzing the temperature dependence of the optoelectronic properties of perovskite lead halide nanocrystals.

Local Rearrangement of the Iodide Defect Structure Determines the Phase Segregation Effect in Mixed-Halide Perovskites.

Mixed-halide perovskites represent a particularly relevant case within the family of lead-halide perovskites. Beyond their technological relevance for a variety of optoelectronic devices, photoinduced structural changes characteristic of this type of material lead to extreme photophysical changes that are currently the subject of intense debate. Herein we show that the conspicuous photoinduced phase segregation characteristic of these materials is primarily the result of the local and metastable rearrangement of the iodide sublattice. A local photophysical study comprising spectrally resolved laser scanning confocal microscopy is employed to find a correlation between the defect density and the dynamics of photoinduced changes, which extend far from the illuminated region. We observe that iodide-rich regions evolve much faster from highly defective regions. Also, by altering the material composition, we find evidence for the interplay between the iodide-related defect distribution and the intra- and interdomain migration dynamics giving rise to the complexity of this process.

Optical Responses of Localized and Extended Modes in a Mesoporous Layer on Plasmonic Array to Isopropanol Vapor.

Mesoporous silica features open and accessible pores that can intake substances from the outside. The combination of mesoporous silica with plasmonic nanostructures represents an interesting platform for an optical sensor based on the dependence of plasmonic modes on the refractive index of the medium in which metallic nanoparticles are embedded. However, so far only a limited number of plasmonic nanostructures are combined with mesoporous silica, including random dispersion of metallic nanoparticles and flat metallic thin films. In this study, we make a mesoporous silica layer on an aluminum nanocylinder array. Such plasmonic arrangements support both localized surface plasmon resonances (LSPRs) and extended modes which are the result of the hybridization of LSPRs and photonic modes extending into the mesoporous layer. We investigate in situ optical reflectance of this system under controlled pressure of isopropanol vapor. Upon exposure, the capillary condensation in the mesopores results in a gradual spectral shift of the reflectance. Our analysis demonstrates that such shifts depend largely on the nature of the modes; that is, the extended modes show larger shifts compared to localized ones. Our materials represent a useful platform for the field of environmental sensing.

Dipole reorientation and local density of optical states influence the emission of light-emitting electrochemical cells.

Herein, we analyze the temporal evolution of the electroluminescence of light-emitting electrochemical cells (LECs), a thin-film light-emitting device, in order to maximize the luminous power radiated by these devices. A careful analysis of the spectral and angular distribution of the emission of LECs fabricated under the same experimental conditions allows describing the dynamics of the spatial region from which LECs emit, i.e. the generation zone, as bias is applied. This effect is mediated by dipole reorientation within such an emissive region and its optical environment, since its spatial drift yields a different interplay between the intrinsic emission of the emitters and the local density of optical states of the system. Our results demonstrate that engineering the optical environment in thin-film light-emitting devices is key to maximize their brightness.

Casimir-Lifshitz Force Based Optical Resonators.

We theoretically investigate the building of optical resonators based on the levitation properties of thin films subjected to strong repulsive Casimir-Lifshitz forces when immersed in an adequate medium and confronted with a planar substrate. We propose a design in which cavities supporting high Q-factor optical modes at visible frequencies can be achieved by means of combining commonly found materials, such as silicon oxide, polystyrene or gold, with glycerol as a mediating medium. We use the balance between flotation and repulsive Casimir-Lifshitz forces in the system to accurately tune the optical cavity thickness and hence its modes. The effects of other forces, such as electrostatic, that may come into play are also considered. Our results constitute a proof of concept that may open the route to the design of photonic architectures in environments in which dispersion forces play a substantial role and could be of particular relevance for devising novel microfluidic optical resonators.

Tamm Plasmons Directionally Enhance Rare-Earth Nanophosphor Emission.

Rare-earth-based phosphors are the materials on which current solid-state lighting technology is built. However, their large crystal size impedes the tuning, optimization, or manipulation of emitted light that can be achieved by their integration in nanophotonic architectures. Herein we demonstrate a hybrid plasmonic-photonic architecture capable of both channeling in a specific direction and enhancing by eight times the emission radiated by a macroscopically wide layer of nanophosphors. In order to do so, a slab of rare-earth-based nanocrystals is inserted between a dielectric multilayer and a metal film, following a rational design that optimizes the coupling of nanophosphor emission to collective modes sustained by the metal-dielectric system. Our approach is advantageous for the optimization of solid-state lighting systems.

Flexible nanophosphor films doped with Mie resonators for enhanced out-coupling of the emission.

Herein, we present a general method to prepare self-standing flexible photoluminescent coatings of controlled opacity for integration into light-emitting diodes (LEDs) employing cost-effective solution-processing methods. From colloidal suspensions of nano-sized phosphors, we fabricate light-emitting transparent films that can be doped with spherical scatterers, which act as Mie resonators that trigger a controlled photoluminescence enhancement, evidenced by the reduction of the guided light along the layer. This results in an enhanced emission compared to that extracted from a bare phosphor layer. We show not only that emission is visible under ultraviolet-LED illumination for both rigid and flexible versions of the coatings, but we also prove the feasibility of the integration of these flexible conversion layers into such devices. We believe these results can contribute to develop more efficient and cost-effective illumination sources by providing efficient and easy-to-handle conversion layers susceptible to excitation by LEDs emitting at wavelengths in the near UV region.