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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.

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

Herein we provide direct experimental evidence that proves that the photophysical properties of thin methylammonium lead iodide perovskite films are significantly enhanced by localized surface plasmon resonances (SPRs). Observations are well supported by rigorous calculations that prove that improved light harvesting can be unequivocally attributed to plasmonic scattering and near field reinforcement effects around silver nanoparticles embedded within the semiconductor layer. Adequate design of the localized SPR allows raising the absorptance of a 300 nm thick film at well-defined spectral regions while minimizing the parasitic absorption from the metallic inclusions. Measured enhancements can be as large as 80% at specific wavelengths and 20% when integrated over the whole range at which SPR occurs, in agreement with theoretical estimations. Simultaneously, the characteristic quenching effect that the vicinity of metals has on the photoluminescence of semiconductors is largely compensated for by the combined effect of the enhanced photoexcitation and the higher local density of photon states occurring at SPR frequencies, with a two fold increase of the perovskite photoemission efficiency being measured.

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.

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 to disentangle the optical constants of the organic capping 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 with 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.

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.

Considering ice-premelting on a quartz rock surface (i.e. silica) we calculate the Lifshitz excess pressures in a four layer system with rock¿ice¿water¿air. Our calculations give excess pressures across (1) ice layer, (2) water layer, and (3) ice¿water interface for different ice and water layer thicknesses. We analyse equilibrium conditions where the different excess pressures take zero value, stabilized in part by repulsive Lifshitz interactions. In contrast to previous investigations which considered varying thickness of only one layer (ice or water), here we present theory allowing for simultaneous variation of both layer thicknesses. For a given total thickness of ice and water, this allows multiple alternative equilibrium solutions. Consequently the final state of a system will depend on initial conditions and may explain variation in experimental measurements of the thicknesses of water and ice layers.

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.

The recent success of perovskite solar cells is based on two solid pillars: the rapid progress of their power conversion efficiency and their flexibility in terms of optoelectrical properties and processing methods. That versatility makes these devices ideal candidates for multi-junction photovoltaics. We report an optically optimized double junction CH3NH3PbI3–CH3NH3PbI3 tandem solar cell where the matched short-circuit current is maximized while parasitic absorption is minimized. The use of an additive vacuum-deposition protocol allows us to reproduce calculated stack designs, which comprise several charge selective materials that ensure appropriate band alignment and charge recombination. This rationalized configuration yields an unprecedented open circuit voltage of 2.30 V. Furthermore, this tandem solar cell features efficiencies larger than 18%, higher than those of the individual sub-cells. Low photo-current values allow reducing the losses associated to the series resistance of transparent contacts, which opens the door to the realization of efficient large area modules.

Nanophosphor integration in an optical cavity allows unprecedented control over both the chromaticity and the directionality of the emitted light, without modifying the chemical composition of the emitters or compromising their efficiency. Our approach opens a route towards the development of nanoscale photonics based solid state lighting.

In spite of the impressive efficiencies reported for perovskite solar cells (PSCs), key aspects of their working principles, such as electron injection at the contacts or the suitability of the utilization of a specific scaffold layer, are not yet fully understood. Increasingly complex scaffolds attained by the sequential deposition of TiO2 and SiO2 mesoporous layers onto transparent conducting substrates are used to perform a systematic characterization of both the injection process at the electron selective contact and the scaffold effect in PSCs. By forcing multiple electron injection processes at a controlled sequence of perovskite–TiO2 interfaces before extraction, interfacial injection effects are magnified and hence characterized in detail. An anomalous injection behavior is observed, the fingerprint of which is the presence of significant inductive loops in the impedance spectra with a magnitude that correlates with the number of interfaces in the scaffold. Analysis of the resistive and capacitive behavior of the impedance spectra indicates that the scaffolds could hinder ion migration, with positive consequences such as lowering the recombination rate and implications for the current–potential curve hysteresis. Our results suggest that an appropriate balance between these advantageous effects and the unavoidable charge transport resistive losses introduced by the scaffolds will help in the optimization of PSC performance.

Organic–inorganic perovskite structures in which lead is substituted by tin are exceptional candidates for broadband light absorption. Herein we present a thorough analysis of the optical properties of CH3NH3SnxPb1−xI3 films, providing the field with definitive insights about the possibilities of these materials for perovskite solar cells of superior efficiency. We report a user's guide based on the first set of optical constants obtained for a series of tin/lead perovskite films, which was only possible to measure due to the preparation of optical quality thin layers. According to the Shockley–Queisser theory, CH3NH3SnxPb1−xI3 compounds promise a substantial enhancement of both short circuit photocurrent and power conversion efficiency in single junction solar cells. Moreover, we propose a novel tandem architecture design in which both top and bottom cells are made of perovskite absorbers. Our calculations indicate that such perovskite-on-perovskite tandem devices could reach efficiencies over 35%. Our analysis serves to establish the first roadmap for this type of cells based on actual optical characterization data. We foresee that this study will encourage the research on novel near-infrared perovskite materials for photovoltaic applications, which may have implications in the rapidly emerging field of tandem devices

We demonstrate that a combined optimization approach based on the sequential alternation of theoretical analysis and experimental realization gives rise to plastic supported dye solar cells for which both light harvesting efficiency and electron collection are maximized. Rationalized configurations with optimized light trapping and charge extraction are realized to achieve photoanodes on plastic prepared at low temperature, showing a power conversion efficiency of 8.55% and a short circuit photocurrent of 16.11 mA cm 2, unprecedented for plastic based dye solar cell devices. Furthermore, the corresponding fully flexible designs present stable mechanical properties after several bending cycles, displaying 7.79% power conversion efficiency, an average broadband internal quantum efficiency above 90%, and a short circuit photocurrent of 15.94 mA cm 2, which is the largest reported value for bendable cells of this sort to date

We have developed a method to alternate porous and dense dielectric films in order to build high refractive index contrast distributed Bragg reflectors (DBRs) capable of reflecting very efficiently in a targeted spectral range employing a small number of layers in the stack. Porous layers made of SiO2 nanoparticles and compact sol–gel processed TiO2 layers are sequentially deposited. The key to the preservation of porosity of every other layer during the deposition process is the use of a sacrificial layer of polystyrene that prevents the infiltration of the interstitial voids between nanoparticles with the homogeneous solution of TiO2 precursors. Our approach allows preparing a series of DBRs operating along the whole visible spectral range. Reflectance values as high as 90% are achieved from only seven layers. The particular distribution of porosity along one direction gives rise to an interesting interplay between the optical properties of the system and the vapor pressure in the surrounding atmosphere, which we foresee could be put into practice in gas sensing devices

Herein we realize an optical design that optimizes the performance of bifacial solar cells without modifying any of the usually employed components. In order to do so, dielectric scatterers of controlled size and shape have been successfully integrated in the working electrodes of dye-sensitized solar cells (DSSCs), resulting in bifacial devices of outstanding performance. Power conversion efficiencies (PCEs) as high as 6.7% and 5.4% have been attained under front and rear illumination, respectively, which represent a 25% and a 33% PCE enhancement with respect to an 8 mm-thick standard solar cell electrode using platinum as the catalytic material. The remarkable bifacial character of our approach is demonstrated by the high rear/front efficiency ratio attained, around 80%, which is among the largest reported for this sort of device. The proposed optimized design is based on a Monte Carlo approach in which the multiple scattering of light within the cell is fully accounted for. We identified that the spherical shape of the scatterers is the key parameter controlling the angular distribution of the scattering, the most efficient devices being those in which the inclusions provide a narrow forward-oriented angular distribution of the scattered light.

Herein we show a solution based synthetic pathway to obtain a resonant optical cavity with embedded colloidal semiconductor quantum dots (CSQDs). The optical cavity pore network, surrounded by two dense Bragg mirrors, was designed ad hoc to selectively host the quantum dots, while uncontrolled infiltration of those in the rest of the layered structure was prevented. Coupling between the optical resonant modes of the host and the natural emission of the embedded nanoparticles gives rise to the fine tuning of the luminescence spectrum extracted from the ensemble. Our approach overcomes, without the need for an encapsulating agent and exclusively by solution processing, the difficulties that arise from the low thermal and chemical stability of the CSQDs. It opens the route to achieving precise control over their location and hence over the spectral properties of light emitted by these widely employed nanomaterials. Furthermore, as the porosity of the cavity is preserved after infiltration, the system remains responsive to environmental changes, which provides an added value to the proposed structure

In order to enhance optical absorption, light trapping by multiple scattering is commonly achieved in dye sensitized solar cells by adding particles of a different sort. Herein we propose a theoretical method to find the structural parameters (particle number density and size) that optimize the conversion efficiency of electrodes of different thicknesses containing spherical inclusions of diverse composition. Our work provides a theoretical framework in which the response of solar cells containing diffuse scattering particles can be rationalized. Optical simulations are performed by combining a Monte Carlo approach with Mie theory, in which the angular distribution of scattered light is accounted for. Several types of scattering centers, such as anatase, gold and silver particles, as well as cavities, are considered and their effect compared. Estimates of photovoltaic performance, insight into the physical mechanisms responsible for the observed enhancements, and guidelines to improve the cell design are provided. We discuss the results in terms of light transport in weakly disordered optical media and find that the observed variations between the optimum scattering configurations attained for different electrode thicknesses can be understood as the result of the randomization of the light propagation direction at different depths within the active layer. A primary conclusion of our study is that photovoltaic performance is optimised when the scattering properties of the film are adjusted so that the distance over which incident photons are randomized is comparable to the thickness of the film. This simple relationship could also be used as a design rule to attain the optimum optical design in other photovoltaic materials. This journal is © The Royal Society of Chemistry.

A panchromatic specular reflector based dye solar cell is herein presented. Photovoltaic performance of this novel design is compared to that of cells in which standard diffuse scattering layers are integrated. The capability of the proposed multilayer structures to both emulate the broad band reflection of diffuse scattering layers of standard thickness (around 5 microns) and give rise to similarly high light harvesting and power conversion efficiencies, yet preserving the transparency of the device, is demonstrated. Such white light reflectors are comprised of stacks of different porous optical multilayers, each one displaying a strong reflection at a complementary spectral range, and are designed to leave transmittance unaltered in a narrow red-frequency range at which the sensitized electrode shows negligible absorption, thus allowing to see through the cell. The reflectance bandwidth achieved is three times as broad as the largest previously achieved with any photonic structure integrated in a dye solar cell.

Herein we report an experimental analysis of the performance of photonic crystal based dye solar cells (PCDSCs) as the incident light angle moves away from the normal with respect to the cell surface. Nanoparticle multilayers operating at different wavelength ranges were coupled to the working electrode of a dye solar cell for this study. The interplay between optical and photovoltaic properties with the incident light angle is discussed.We demonstrate that an efficiency enhancement is attained for PC-DSCs at all angles measured, and that rational design of the photonic crystal back mirror leads to a reduction of the photocurrent losses related to the tilt angle of the cell, usually labeled as cosine losses. Angular variations of the cell transparency are also reported and discussed. These angular properties are relevant to the application of these solar devices in building integrated photovoltaics as potential window modules.

Herein we analyze experimentally the effect that introducing highly reflecting photonic crystals, operating at different spectral ranges, has on the conversion efficiency of dye sensitized solar cells. The interplay between structural colour and cell performance is discussed on the basis of the modified spectral response of the photogenerated current observed and the optical characterization of the cells. We demonstrate that, with the approach herein discussed, it is possible to achieve relatively high efficiencies using thin electrodes while preserving transparency. At the same time, the appearance of the device can be controllably modified, which is of relevance for their potential application in building integrated photovoltaics (BIPV) as window modules. This journal is © The Royal Society of Chemistry 2012.

Herein we demonstrate improved mass transport through nanoparticle one-dimensional photonic crystals of enhanced porosity. Analysis is made by impedance spectroscopy using iodine and ionic liquid based electrolytes and shows that newly created large pores and increased porosity improve the diffusion of species through the photonic crystal. This achievement is based on the use of a polymeric porogen (polyethylene glycol), which is mixed with the precursor suspensions used for the deposition of nanoparticle TiO2 and SiO2 layers and then eliminated to generate a more open interconnected void network, as confirmed by specular reflectance porosimetry . A compromise between pore size and optical quality of these periodic structures is found.

In recent times, several synthetic pathways have been developed to create multilayered materials of diverse composition that combine accessible porosity and optical properties of structural origin, i.e., not related to absorption. These materials possess a refractive index that varies periodically along one direction, which gives rise to optical diffraction effects characteristic of Bragg stacks or one-dimensional photonic crystals (1DPCs). The technological potential of such porous optical materials has been demonstrated in various fields related to energy and environmental sciences, such as detection and recognition of targeted biological or chemical species, photovoltaics, or radiation shielding. In all cases, improved performance is achieved as a result of the added functionality porosity brings. In this review, a unified picture of this emerging field is provided.

Herein we present a synthetic route to attain porous one-dimensional photonic crystals of high optical quality. The method employed, based on the alternate deposition of TiO2 and SiO2 porous layers by glancing angle physical vapour deposition, yields a highly accessible interconnected pore network throughout the entire multilayer structure. Furthermore, it allows a strict control over the average size and density of the interstitial sites, which results in the precise tuning of the refractive index of the individual layers and thus of the optical response of the ensemble. The controlled environmental response of the multilayer is confirmed by the optical monitoring of the infiltration of liquids of different refractive index. © 2010 The Royal Society of Chemistry.

In this work, we demonstrate that optical resonators built using all-nanoparticle-based porous building blocks provide a responsive multifunctional matrix, totally different emission spectra being attained from the same embedded luminescent nanophosphors under varying environmental conditions. We show a clear correlation between modifications in the ambient surroundings, the induced changes of the resonant modes, and the resulting variations in the emission response. The method is versatile and allows nanophosphors of arbitrary shape to be integrated in the cavity. By precise control of the spectral features of the optical resonances, luminescence is strongly modulated in selected and tuneable wavelength ranges. Applications in the fields of sensing and detection are foreseen for these materials. © 2010 The Royal Society of Chemistry.

The use of both supported and flexible self-standing nanoparticle-based one dimensional photonic crystal films as effective frequency selective filters in the UV-vis-NIR is herein evaluated. The requirements to achieve a flat spectral response at the desired frequency range are analyzed and a synthetic route to realize materials with such properties presented. Strict control over the structural parameters yields multilayers in which the opening or closing of higher order photonic band gaps can be devised, thus leading to films capable of blocking the UV and NIR ranges simultaneously. Furthermore, the physico-chemical properties of the mirror can be modified to yield either moisture-repelling or, on the contrary, environmentally responsive optical filters. These materials present a great potential to be used as versatile and multifunctional optical elements. © 2010 The Royal Society of Chemistry.

Recent advances in the comprehension of the growth dynamics of colloidal crystal films opens the door to rational design of experiments aiming at fabricating lattices in which the density of intrinsic defects is minimized. Since such imperfections have a dramatic effect on scattered light of wavelength smaller than the lattice constant, the evaluation of the experimental optical response at those energy ranges, based on the comparison to rigorous calculations, is identified as the most sensitive guide to accurately evaluate the progress towards the actual realization of defect-free colloidal crystals. © 2009 The Royal Society of Chemistry.

Self-standing, flexible Bragg mirror films of high refractive index contrast and showing intense and wide Bragg peaks are herein presented. Nanoparticle-based one-dimensional photonic crystals are used as templates to infiltrate a polymer, which provides the multilayer with mechanical stability while preserving the dielectric contrast existing in the mold. Such films can be lifted off the substrate and used to coat another surface of arbitrary shape. © The Royal Society of Chemistry 2009.

Polyferrocenylsilane gel photonic crystals have been reversibly swollen using solvent vapors, and exhibit precise pressure tunability over a wavelength range of greater than 100 nm