Enhancement of the internal quantum efficiency in strongly coupled P3HT-C60 organic photovoltaic cells using Fabry-Perot cavities with varied cavity confinement.

The short exciton diffusion length in organic semiconductors results in a strong dependence of the conversion efficiency of organic photovoltaic (OPV) cells on the morphology of the donor-acceptor bulk-heterojunction blend. Strong light-matter coupling provides a way to circumvent this dependence by combining the favorable properties of light and matter via the formation of hybrid exciton-polaritons. By strongly coupling excitons in P3HT-C60 OPV cells to Fabry-Perot optical cavity modes, exciton-polaritons are formed with increased propagation lengths. We exploit these exciton-polaritons to enhance the internal quantum efficiency of the cells, determined from the external quantum efficiency and the absorptance. Additionally, we find a consistent decrease in the Urbach energy for the strongly coupled cells, which indicates the reduction of energetic disorder due to the delocalization of exciton-polaritons in the optical cavity.

Refractive index sensing using quasi-bound states in the continuum in silicon metasurfaces.

This work presents a bulk refractive index sensor based on quasi-bound states in the continuum (BICs) induced by broken symmetries in metasurfaces. The symmetry is broken by detuning the size and position of silicon particles periodically arranged in an array, resulting in multiple quasi-BIC resonances. We investigate the sensing characteristics of each of the resonances by measuring the spectral shift in response to changes in the refractive index of the surrounding medium. In addition, we reveal the sensing range of the different resonances through simulations involving a layer of deviating refractive index of increasing thickness. Interestingly, the resonances show very different responses, which we describe via the analysis of the near-field. This work contributes to the development of highly sensitive and selective BIC-based sensors that can be used for a wide range of applications.

Tunable emission from H-type supramolecular polymers in optical nanocavities.

H-type supramolecular polymers with preferred helicity and highly efficient emission have been prepared from the self-assembly of chiral tetraphenylene-based monomers. Implementation of the one-dimensional fibers into dielectric nanoparticle arrays allows for a significant reshaping of fluorescence due to weak light-matter coupling.

The Rise and Current Status of Polaritonic Photochemistry and Photophysics.

The interaction between molecular electronic transitions and electromagnetic fields can be enlarged to the point where distinct hybrid light-matter states, polaritons, emerge. The photonic contribution to these states results in increased complexity as well as an opening to modify the photophysics and photochemistry beyond what normally can be seen in organic molecules. It is today evident that polaritons offer opportunities for molecular photochemistry and photophysics, which has caused an ever-rising interest in the field. Focusing on the experimental landmarks, this review takes its reader from the advent of the field of polaritonic chemistry, over the split into polariton chemistry and photochemistry, to present day status within polaritonic photochemistry and photophysics. To introduce the field, the review starts with a general description of light-matter interactions, how to enhance these, and what characterizes the coupling strength. Then the photochemistry and photophysics of strongly coupled systems using Fabry-Perot and plasmonic cavities are described. This is followed by a description of room-temperature Bose-Einstein condensation/polariton lasing in polaritonic systems. The review ends with a discussion on the benefits, limitations, and future developments of strong exciton-photon coupling using organic molecules.

Thickness-dependent Auger scattering in a single WS2 microcrystal probed with time-resolved terahertz near-field microscopy.

Time-resolved terahertz (THz) spectroscopy has been shown as a powerful technique to non-invasively determine the charge carrier properties in photoexcited semiconductors. However, the long wavelengths of terahertz radiation reduce the applicability of this technique to large samples. Using THz near-field microscopy, we show THz measurements of the lifetime of 2D single exfoliated microcrystals of transition metal dichalcogenides (WS2). The increased spatial resolution of THz near-field microscopy allows spatial mapping of the evolution of the carrier lifetime, revealing Auger assisted surface defect recombination as the dominant recombination channel. THz near-field microscopy allows for the non-invasive and high-resolution investigation of material properties of 2D semiconductors relevant for nanoelectronic and optoelectronic applications.

Inverse designed plasmonic metasurface with parts per billion optical hydrogen detection.

Plasmonic sensors rely on optical resonances in metal nanoparticles and are typically limited by their broad spectral features. This constraint is particularly taxing for optical hydrogen sensors, in which hydrogen is absorbed inside optically-lossy Pd nanostructures and for which state-of-the-art detection limits are only at the low parts-per-million (ppm) range. Here, we overcome this limitation by inversely designing a plasmonic metasurface based on a periodic array of Pd nanoparticles. Guided by a particle swarm optimization algorithm, we numerically identify and experimentally demonstrate a sensor with an optimal balance between a narrow spectral linewidth and a large field enhancement inside the nanoparticles, enabling a measured hydrogen detection limit of 250 parts-per-billion (ppb). Our work significantly improves current plasmonic hydrogen sensor capabilities and, in a broader context, highlights the power of inverse design of plasmonic metasurfaces for ultrasensitive optical (gas) detection.

Controlling Exciton Propagation in Organic Crystals through Strong Coupling to Plasmonic Nanoparticle Arrays.

Exciton transport in most organic materials is based on an incoherent hopping process between neighboring molecules. This process is very slow, setting a limit to the performance of organic optoelectronic devices. In this Article, we overcome the incoherent exciton transport by strongly coupling localized singlet excitations in a tetracene crystal to confined light modes in an array of plasmonic nanoparticles. We image the transport of the resulting exciton-polaritons in Fourier space at various distances from the excitation to directly probe their propagation length as a function of the exciton to photon fraction. Exciton-polaritons with an exciton fraction of 50% show a propagation length of 4.4 µm, which is an increase by 2 orders of magnitude compared to the singlet exciton diffusion length. This remarkable increase has been qualitatively confirmed with both finite-difference time-domain simulations and atomistic multiscale molecular dynamics simulations. Furthermore, we observe that the propagation length is modified when the dipole moment of the exciton transition is either parallel or perpendicular to the cavity field, which opens a new avenue for controlling the anisotropy of the exciton flow in organic crystals. The enhanced exciton-polariton transport reported here may contribute to the development of organic devices with lower recombination losses and improved performance.

Evolutionary optimization of light-matter coupling in open plasmonic cavities.

Using a particle swarm optimization algorithm and finite-difference in time-domain simulations, we optimize the coupling strength between excitons in poly(3-hexylthiophene-2,5-diyl) (P3HT) and surface lattice resonances in open cavities defined by arrays of aluminum nanoparticles. Strong light-matter coupling and the formation of exciton-polaritons are demonstrated. Nanoparticle arrays with optimal dimensions have been fabricated and measured, validating the predictions by the numerical method. P3HT is a regioregular semiconducting polymer used as a donor material in acceptor-donor blends for organic photovoltaic applications. Our results demonstrate the efficacy of the proposed method for the optimization of light-matter coupling and its potential application for the enhanced performance of optoelectronic devices.

Highly Ordered 2D-Assemblies of Phase-Segregated Block Molecules for Upconverted Linearly Polarized Emission.

Materials based on the laminar ordering of self-assembled molecules have a unique potential for applications requiring efficient energy migration through densely packed chromophores. Here, employing molecular assemblies of coil-rod-coil block molecules for triplet-triplet annihilation upconversion (TTA-UC) based on triplet energy migration with linearly polarized emission is reported. By covalently attaching discrete-length oligodimethylsiloxane (oDMS) to 9,10-diphenylanthracene (DPA), highly ordered 2D crystalline DPA sheets separated by oDMS layers are obtained. Transparent films of this material doped with small amounts of triplet sensitizer PtII octaethylporphyrin show air-stable TTA-UC under non-coherent excitation. Upon annealing, an increase in TTA-UC up to two orders of magnitude is observed originating from both an improved molecular ordering of DPA and an increased dispersion of the sensitizer. The molecular alignment in millimeter-sized domains leads to upconverted linearly polarized emission without alignment layers. By using a novel technique, upconversion imaging microscopy, the TTA-UC intensity is spatially resolved on a micrometer scale to visually demonstrate the importance of molecular dispersion of sensitizer molecules for efficient TTA-UC. The reported results are promising for anti-counterfeiting and 3D night-vision applications, but also exemplify the potential of discrete oligodimethylsiloxane functionalized chromophores for highly aligned and densely packed molecular materials.

Super-resolution Mapping of Enhanced Emission by Collective Plasmonic Resonances.

Plasmonic particle arrays have remarkable optical properties originating from their collective behavior, which results in resonances with narrow line widths and enhanced electric fields extending far into the surrounding medium. Such resonances can be exploited for applications in strong light-matter coupling, sensing, light harvesting, nonlinear nanophotonics, lasing, and solid-state lighting. However, as the lattice constants associated with plasmonic particle arrays are on the order of their resonance wavelengths, mapping the interaction between point dipoles and plasmonic particle arrays cannot be done with diffraction-limited methods. Here, we map the enhanced emission of single fluorescent molecules coupled to a plasmonic particle array with ∼20 nm in-plane resolution by using stochastic super-resolution microscopy. We find that extended lattice resonances have minimal influence on the spontaneous decay rate of an emitter but instead can be exploited to enhance the outcoupling and directivity of the emission. Our results can guide the rational design of future optical devices based on plasmonic particle arrays.

Nonlinear Emission of Molecular Ensembles Strongly Coupled to Plasmonic Lattices with Structural Imperfections.

We demonstrate nonlinear emission from molecular layers strongly coupled to extended light fields in arrays of plasmonic nanoparticles in the presence of structural imperfections. Hybrid light-matter states, known as plasmon-exciton polaritons (PEPs), are formed by the strong coupling of Frenkel excitons in molecules to surface lattice resonances. These resonances result from the radiative coupling of localized surface plasmon polaritons in silver nanoparticles enhanced by diffraction on the array. By designing arrays with different lattice constants, we show that the nonlinear emission frequency is solely determined by the relaxation of exciton polaritons through vibrational quanta in the molecules. We also observe long-range spatial coherence in the samples, which supports the explanation in terms of a nonlinear collective emission of strongly coupled PEPs. In contrast to recent observations of exciton-polariton lasing and condensation in organic systems, photonic modes play a minor role at the emission frequency in our system, and this emission has an undefined momentum because of the structural imperfections. This remarkable result reveals the rich and distinct physics of strongly coupled organic molecules to photonic cavities.

High-Efficiency Nanowire Solar Cells with Omnidirectionally Enhanced Absorption Due to Self-Aligned Indium-Tin-Oxide Mie Scatterers.

Photovoltaic cells based on arrays of semiconductor nanowires promise efficiencies comparable or even better than their planar counterparts with much less material. One reason for the high efficiencies is their large absorption cross section, but until recently the photocurrent has been limited to less than 70% of the theoretical maximum. Here we enhance the absorption in indium phosphide (InP) nanowire solar cells by employing broadband forward scattering of self-aligned nanoparticles on top of the transparent top contact layer. This results in a nanowire solar cell with a photovoltaic conversion efficiency of 17.8% and a short-circuit current of 29.3 mA/cm2 under 1 sun illumination, which is the highest reported so far for nanowire solar cells and among the highest reported for III-V solar cells. We also measure the angle-dependent photocurrent, using time-reversed Fourier microscopy, and demonstrate a broadband and omnidirectional absorption enhancement for unpolarized light up to 60° with a wavelength average of 12% due to Mie scattering. These results unambiguously demonstrate the potential of semiconductor nanowires as nanostructures for the next generation of photovoltaic devices.

Metallic nanostructures for efficient LED lighting.

Light-emitting diodes (LEDs) are driving a shift toward energy-efficient illumination. Nonetheless, modifying the emission intensities, colors and directionalities of LEDs in specific ways remains a challenge often tackled by incorporating secondary optical components. Metallic nanostructures supporting plasmonic resonances are an interesting alternative to this approach due to their strong light-matter interaction, which facilitates control over light emission without requiring external secondary optical components. This review discusses new methods that enhance the efficiencies of LEDs using nanostructured metals. This is an emerging field that incorporates physics, materials science, device technology and industry. First, we provide a general overview of state-of-the-art LED lighting, discussing the main characteristics required of both quantum wells and color converters to efficiently generate white light. Then, we discuss the main challenges in this field as well as the potential of metallic nanostructures to circumvent them. We review several of the most relevant demonstrations of LEDs in combination with metallic nanostructures, which have resulted in light-emitting devices with improved performance. We also highlight a few recent studies in applied plasmonics that, although exploratory and eminently fundamental, may lead to new solutions in illumination.

Hybrid Semiconductor Nanowire-Metallic Yagi-Uda Antennas.

We demonstrate the directional emission of individual GaAs nanowires by coupling this emission to Yagi-Uda optical antennas. In particular, we have replaced the resonant metallic feed element of the nanoantenna by an individual nanowire and measured with the microscope the photoluminescence of the hybrid structure as a function of the emission angle by imaging the back focal plane of the objective. The precise tuning of the dimensions of the metallic elements of the nanoantenna leads to a strong variation of the directionality of the emission, being able to change this emission from backward to forward. We explain the mechanism leading to this directional emission by finite difference time domain simulations of the scattering efficiency of the antenna elements. These results cast the first step toward the realization of electrically driven optical Yagi-Uda antenna emitters based on semiconductors nanowires.

Directional and Polarized Emission from Nanowire Arrays.

Lighting applications require directional and polarization control of the emitted light, which is currently achieved by bulky optical components such as lenses, parabolic mirrors, and polarizers. Ideally, this control would be achieved without any external optics, but at the nanoscale, during the generation of light. Semiconductor nanowires are promising candidates for lighting devices due to their efficient light outcoupling and synthesis flexibility. In this work, we demonstrate a precise control of both the directionality and the polarization of the nanowire array emission by changing the nanowire diameter. We change the angular emission pattern from a large-angle doughnut shape to a narrow-angle beaming along the nanowire axis. In addition, we tune the polarization from unpolarized to either p- or s-polarized. Both the far-field emission pattern and its polarization are controlled by the number and type of guided or leaky modes supported by the nanowire, which are determined by the nanowire diameter.

Active liquid crystal tuning of metallic nanoantenna enhanced light emission from colloidal quantum dots.

A system comprising an aluminum nanoantenna array on top of a luminescent colloidal quantum dot waveguide and covered by a thermotropic liquid crystal (LC) is introduced. By heating the LC above its critical temperature, we demonstrate that the concomitant refractive index change modifies the hybrid plasmonic-photonic resonances in the system. This enables active control of the spectrum and directionality of the narrow-band (∼6 nm) enhancement of quantum dot photoluminescence by the metallic nanoantennas.

Coherent and broadband enhanced optical absorption in graphene.

We experimentally demonstrate a broadband enhancement of the light absorption in graphene over the whole visible spectrum. This enhanced absorption is obtained in a multilayer structure by using an Attenuated Total Reflectance (ATR) configuration and it is explained in terms of coherent absorption arising from interference and dissipation. The interference mechanism leading to the phenomenon of coherent absorption allows for its precise control by varying the refractive index and/or thickness of the medium surrounding the graphene.

Nanowire antenna emission.

We experimentally demonstrate the directional emission of polarized light from single semiconductor nanowires. The directionality of this emission has been directly determined with Fourier microphotoluminescence measurements of vertically oriented InP nanowires. Nanowires behave as efficient optical nanoantennas, with emission characteristics that are not only given by the material but also by their geometry and dimensions. By means of finite element simulations, we show that the radiated power can be enhanced for frequencies and diameters at which leaky modes in the structure are present. These leaky modes can be associated to Mie resonances in the cylindrical structure. The radiated power can be also inhibited at other frequencies or when the coupling of the emission to the resonances is not favored. We anticipate the relevance of these results for the development of nanowire photon sources with optimized efficiency and/or controlled emission by the geometry.

Surface wave sensors based on nanometric layers of strongly absorbing materials.

We demonstrate the excitation of guided modes in thin layers of strongly absorbing chalcogenide glasses. These modes are similar to surface plasmon polaritons in terms of resonance width and shift with changes in the permittivity of the surrounding medium. We exploit these characteristics to demonstrate a high sensitivity chalcogenide glass refractive index sensor that outperforms gold surface plasmon resonance sensors at short wavelengths in the visible. This demonstration opens a new range of possibilities for sensing using different materials.