Microconical silicon mid-IR concentrators: spectral, angular and polarization response.

It is widely discussed in the literature that a problem of reduction of thermal noise of mid-wave and long-wave infrared (MWIR and LWIR) cameras and focal plane arrays (FPAs) can be solved by using light-concentrating structures. The idea is to reduce the area and, consequently, the thermal noise of photodetectors, while still providing a good collection of photons on photodetector mesas that can help to increase the operating temperature of FPAs. It is shown that this approach can be realized using microconical Si light concentrators with (111) oriented sidewalls, which can be mass-produced by anisotropic wet etching of Si (100) wafers. The design is performed by numerical modeling in a mesoscale regime when the microcones are sufficiently large (several MWIR wavelengths) to resonantly trap photons, but still too small to apply geometrical optics or other simplified approaches. Three methods of integration Si microcone arrays with the focal plane arrays are proposed and studied: (i) inverted microcones fabricated in a Si slab, which can be heterogeneously integrated with the front illuminated FPA photodetectors made from high quantum efficiency materials to provide resonant power enhancement factors (PEF) up to 10 with angle-of-view (AOV) up to 10°; (ii) inverted microcones, which can be monolithically integrated with metal-Si Schottky barrier photodetectors to provide resonant PEFs up to 25 and AOVs up to 30° for both polarizations of incident plane waves; and iii) regular microcones, which can be monolithically integrated with near-surface photodetectors to provide a non-resonant power concentration on compact photodetectors with large AOVs. It is demonstrated that inverted microcones allow the realization of multispectral imaging with ∼100 nm bands and large AOVs for both polarizations. In contrast, the regular microcones operate similar to single-pass optical components (such as dielectric microspheres), producing sharply focused photonic nanojets.

Bright and Ultrafast Photoelectron Emission from Aligned Single-Wall Carbon Nanotubes through Multiphoton Exciton Resonance.

Ultrashort bunches of electrons, emitted from solid surfaces through excitation by ultrashort laser pulses, are an essential ingredient in advanced X-ray sources, and ultrafast electron diffraction and spectroscopy. Multiphoton photoemission using a noble metal as the photocathode material is typically used but more brightness is desired. Artificially structured metal photocathodes have been shown to enhance optical absorption via surface plasmon resonance but such an approach severely reduces the damage threshold in addition to requiring state-of-the-art facilities for photocathode fabrication. Here, we report ultrafast photoelectron emission from sidewalls of aligned single-wall carbon nanotubes. We utilized strong exciton resonances inherent in this prototypical one-dimensional material, and its excellent thermal conductivity and mechanical rigidity leading to a high damage threshold. We obtained unambiguous evidence for resonance-enhanced multiphoton photoemission processes with definite power-law behaviors. In addition, we observed strong polarization dependence and ultrashort photoelectron response time, both of which can be quantitatively explained by our model. These results firmly establish aligned single-wall carbon nanotube films as novel and promising ultrafast photocathode material.

Reversible Circularly Polarized Reflection in a Self-Organized Helical Superstructure Enabled by a Visible-Light-Driven Axially Chiral Molecular Switch.

Development of light-driven functional materials capable of displaying reversible properties is currently a vibrant frontier from both scientific and technological points of view. Here a new visible-light-driven chiral molecular switch is synthesized and characterized. To the best of our knowledge, this is the first example of a chiral molecular switch in which the visible-light-driven azobenzene motif is directly linked to an axially chiral scaffold through a C-C bond. The chiral molecular switch exhibits trans-to- cis photoisomerization upon 530 nm irradiation and cis-to- trans isomerization upon 450 nm irradiation. The switch can thus be photoisomerized in both directions using visible light of different wavelengths, a promising attribute for device applications. It was found that this relatively rigid molecular switch exhibited a high helical twisting power (HTP) in liquid crystal hosts and a large change of HTP value upon photoisomerization. We achieved dynamic reflection tuning across the visible spectrum through incorporation into a self-organized helical superstructure, i.e., a cholesteric liquid crystal. We also demonstrated patterned photodisplays reflecting red, green, and blue circularly polarized light using these cholesteric films. Phototunable color displays were fabricated by selective light irradiation where the information can be reversibly hidden by applying an electric field and restored by applying either a mechanical force or an electric field of higher voltage.

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials.

Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.

Photochemically and Thermally Driven Full-Color Reflection in a Self-Organized Helical Superstructure Enabled by a Halogen-Bonded Chiral Molecular Switch.

Supramolecular approaches toward the fabrication of functional materials and systems have been an enabling endeavor. Recently, halogen bonding has been harnessed as a promising supramolecular tool. Herein we report the synthesis and characterization of a novel halogen-bonded light-driven axially chiral molecular switch. The photoactive halogen-bonded chiral switch is able to induce a self-organized, tunable helical superstructure, that is, cholesteric liquid crystal (CLC), when doped into an achiral liquid crystal (LC) host. The halogen-bonded switch as a chiral dopant has a high helical twisting power (HTP) and shows a large change of its HTP upon photoisomerization. This light-driven dynamic modulation enables reversible selective reflection color tuning across the entire visible spectrum. The chiral switch also displays a temperature-dependent HTP change that enables thermally driven red, green, and blue (RGB) reflection colors in the self-organized helical superstructure.

Photonic jets for highly efficient mid-IR focal plane arrays with large angle-of-view.

One of the trends in design of mid-wave infrared (MWIR) focal plane arrays (FPAs) consists in reduction of the pixel sizes which allows increasing the resolution and decreasing the dark currents of FPAs. To keep high light collection efficiency and to combine it with large angle-of-view (AOV) of FPAs, in this work we propose to use photonic jets produced by the dielectric microspheres for focusing and highly efficient coupling light into individual photodetector mesas. In this approach, each pixel of FPA is integrated with the appropriately designed, fixed and properly aligned microsphere. The tasks consist in developing technology of integration of microspheres with pixels on a massive scale and in developing designs of corresponding structures. We propose to use air suction through a microhole array for assembling ordered arrays of microspheres. We demonstrate that this technology allows obtaining large-scale arrays containing thousands of microspheres with ~1% defect rate which represents a clear advantage over the best results obtained by the techniques of directed self-assembly. We optimized the designs of such FPAs integrated with microspheres for achieving maximal angle of view (AOV) as a function of the index of refraction and diameter of the microspheres. Using simplified two-dimensional finite difference time domain (FDTD) modeling we designed structures where the microspheres are partly-immersed in a layer of photoresist or slightly truncated by using controllable temperature melting effects. Compared to the standard microlens arrays, our designs provide up to an order of magnitude higher AOVs reaching ~8° for back-illuminated and ~20° for front-illuminated structures.

Lasing of surface-polished polycrystalline Ho: YAG (yttrium aluminum garnet) fiber.

A polycrystalline 1.5% Ho: YAG fiber with a diameter of 31 µm was prepared. Surface roughness from grain boundary grooving was reduced by polishing, which decreased the fiber scattering coefficient from 76 m-1 to 35 m-1. Lasing tests were done on this fiber with a SF57 Schott glass cladding. Lasing was confirmed by spectrum narrowing with threshold pump power lower than 500 mW and a slope efficiency of 7%. To our knowledge, this is the first lasing demonstration from a small diameter polycrystalline ceramic fiber.

Overcoming the diffraction limit of imaging nanoplasmonic arrays by microspheres and microfibers.

Super-resolution microscopy by microspheres emerged as a simple and broadband imaging technique; however, the mechanisms of imaging are debated in the literature. Furthermore, the resolution values were estimated based on semi-quantitative criteria. The primary goals of this work are threefold: i) to quantify the spatial resolution provided by this method, ii) to compare the resolution of nanoplasmonic structures formed by different metals, and iii) to understand the imaging provided by microfibers. To this end, arrays of Au and Al nanoplasmonic dimers with very similar geometry were imaged using confocal laser scanning microscopy at λ = 405 nm through high-index (n~1.9-2.2) liquid-immersed BaTiO3 microspheres and through etched silica microfibers. We developed a treatment of super-resolved images in label-free microscopy based on using point-spread functions with subdiffraction-limited widths. It is applicable to objects with arbitrary shapes and can be viewed as an integral form of the super-resolution quantification widely accepted in fluorescent microscopy. In the case of imaging through microspheres, the resolution ~λ/6-λ/7 is demonstrated for Au and Al nanoplasmonic arrays. In the case of imaging through microfibers, the resolution ~λ/6 with magnification M~2.1 is demonstrated in the direction perpendicular to the fiber with hundreds of times larger field-of-view in comparison to microspheres.

Direct measurement of group delay dispersion in metamagnetics for ultrafast pulse shaping.

In this paper, we explore the use of magnetic resonant metamaterials, so called metamagnetics, as dispersive elements for optical pulse shaping. We measure both positive and negative group delay dispersion (GDD) values in a metamagnetic material using the multiphoton interference phase scan (MIIPS) technique and show pulse temporal profiles numerically. The results are compared with finite element models. These GDD properties of metamagnetics, along with previously shown tunability and loss control with gain media, enable their use in ultrashort pulse optical applications.

Plasmonic enhancement of the two photon absorption cross section of an organic chromophore using polyelectrolyte-coated gold nanorods.

The effect of plasmonic enhancement on the two-photon absorption cross section of organic chromophores attached to polyelectrolyte-coated gold nanorods was investigated. The magnitudes of such enhancements were confirmed using single and two photon excitations of the chromophore molecules bound to polyelectrolyte-coated gold nanorods. By synthesizing two-, four-, six-, and eight-polyelectrolyte layer coated nanorods of a particular aspect ratio, the distance dependence of the evanescent electromagnetic field on molecular two-photon absorption was observed. Enhancements of 40-fold were observed for the chromophores nearest to the surface.

High-Efficiency Solar Vapor Generation Boosted by a Solar-Induced Updraft with Biomimetic 3D Structures.

Sunlight-based desalination is one of the most environment-friendly, low-cost methods for obtaining freshwater on the planet. We implemented a biomimetic three-dimensional (3D) solar evaporator, improved by a solar-induced air-flow updraft. A carbon-coated polyvinyl alcohol (PVA) foam allowed us to achieve perfect absorption of ultrabroadband sunlight and continuously provide water to tall 3D structures. Integrating the convection flower (Amorphophallus titanum) and solar chimney structure, we proposed a bio-inspired 3D solar evaporator system that generates an updraft airflow. This updraft replaces saturated vapor between neighboring PVA foams with dry air, resulting in a significant increase in the effectiveness of dry air-water contact interfaces. Under the 1 sun condition (1 kW m-2), we achieve a high solar-vapor conversion efficiency of 95.9%.

Nature-Inspired Emerging Chiral Liquid Crystal Nanostructures: From Molecular Self-Assembly to DNA Mesophase and Nanocolloids.

Liquid crystals (LCs) are omnipresent in living matter, whose chirality is an elegant and distinct feature in certain plant tissues, the cuticles of crabs, beetles, arthropods, and beyond. Taking inspiration from nature, researchers have recently devoted extensive efforts toward developing chiral liquid crystalline materials with self-organized nanostructures and exploring their potential applications in diverse fields ranging from dynamic photonics to energy and safety issues. In this review, an account on the state of the art of emerging chiral liquid crystalline nanostructured materials and their technological applications is provided. First, an overview on the significance of chiral liquid crystalline architectures in various living systems is given. Then, the recent significant progress in different chiral liquid crystalline systems including thermotropic LCs (cholesteric LCs, cubic blue phases, achiral bent-core LCs, etc.) and lyotropic LCs (DNA LCs, nanocellulose LCs, and graphene oxide LCs) is showcased. The review concludes with a perspective on the future scope, opportunities, and challenges in these truly advanced functional soft materials and their promising applications.

Photophysical properties of C60 colloids suspended in water with Triton X-100 surfactant: excited-state properties with femtosecond resolution.

We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.

Visible-Light-Induced Self-Organized Helical Superstructure in Orientationally Ordered Fluids.

Light-induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible-light-induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible-light-driven chiral molecular switch. The cyclic-azobenzene-based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n-π* transitions of its trans- and cis-isomers. Green light (530 nm) drives the trans-to-cis photoisomerization whereas the cis-to-trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light-induced helical superstructure enables the formation of diffraction gratings in cholesteric films.

Dynamic Control of Light Direction Enabled by Stimuli-Responsive Liquid Crystal Gratings.

The ability to control light direction with tailored precision via facile means is long-desired in science and industry. With the advances in optics, a periodic structure called diffraction grating gains prominence and renders a more flexible control over light propagation when compared to prisms. Today, diffraction gratings are common components in wavelength division multiplexing devices, monochromators, lasers, spectrometers, media storage, beam steering, and many other applications. Next-generation optical devices, however, demand nonmechanical, full and remote control, besides generating higher than 1D diffraction patterns with as few optical elements as possible. Liquid crystals (LCs) are great candidates for light control since they can form various patterns under different stimuli, including periodic structures capable of behaving as diffraction gratings. The characteristics of such gratings depend on several physical properties of the LCs such as film thickness, periodicity, and molecular orientation, all resulting from the internal constraints of the sample, and all of these are easily controllable. In this review, the authors summarize the research and development on stimuli-controllable diffraction gratings and beam steering using LCs as the active optical materials. Dynamic gratings fabricated by applying external field forces or surface treatments and made of chiral and nonchiral LCs with and without polymer networks are described. LC gratings capable of switching under external stimuli such as light, electric and magnetic fields, heat, and chemical composition are discussed. The focus is on the materials, designs, applications, and future prospects of diffraction gratings using LC materials as active layers.

Material-Versatile Ultrabroadband Light Absorber with Self-Aggregated Multiscale Funnel Structures.

Broadband light absorbers are essential components for a variety of applications, including energy harvesting and optoelectronic devices. Thus, the development of a versatile absorbing structure that is applicable in various operating environments is required. In this study, a material-versatile ultrabroadband absorber consisting of metal-coated self-aggregated Al2O3 nanowire bundles with multiscale funnel structures is fabricated. A high absorptance of ∼0.9 over the AM 1.5G spectrum (300-2500 nm) is realized for absorbers with a range of metal coatings, including Al, W, and titanium nitride (TiN). We demonstrate that the plasmonic nanofocusing and index-matching effects of the funnel structure result in strong ultrabroadband absorption for the various metal coatings, even though the coating materials have different optical properties. As an example of applicability in an operating environment, in the evaluation of the thermal-oxidation resistance, the Al-coated solar absorber exhibits superior performance to those coated with refractory materials such as W and TiN because of the protective alumina layer formed on the Al surface.

Publisher Correction: Intensity-dependent modulation of optically active signals in a chiral metamaterial.

This corrects the article DOI: 10.1038/ncomms14602.

Cooperative bi-exponential decay of dye emission coupled via plasmons.

Bi-exponential decay of dye fluorescence near the surface of plasmonic metamaterials and core-shell nanoparticles is shown to be an intrinsic property of the coupled system. Indeed, the Dicke, cooperative states involve two groups of transitions: super-radiant, from the most excited to the ground states and sub-radiant, which cannot reach the ground state. The relaxation in the sub-radiant system occurs mainly due to the interaction with the plasmon modes. Our theory shows that the relaxation leads to the population of the sub-radiant states by dephasing the super-radiant Dicke states giving rise to the bi-exponential decay in agreement with the experiments. We use a set of metamaterial samples consisting of gratings of paired silver nanostrips coated with Rh800 dye molecules, having resonances in the same spectral range. The bi-exponential decay is demonstrated for Au\SiO2\ATTO655 core-shell nanoparticles as well, which persists even when averaging over a broad range of the coupling parameter.

Waveguide coupling via magnetic gratings with effective strips.

Gratings with complex multilayer strips are studied under inclined incident light. Great interest in these gratings is due to applications as input/output tools for waveguides and as subwavelength metafilms. The structured strips introduce anisotropy in the effective parameters, providing additional flexibility in polarization and angular dependences of optical responses. Their characterization is challenging in the intermediate regime between subwavelength and diffractive modes. The transition between modes occurs at the Wood's anomaly wavelength, which is different at different angle of incidence. The usual characterization with an effective film using permittivity ε and permeability µ has limited effectiveness at normal incidence but does not apply at inclined illumination, due to the effect of periodicity. The optical properties are better characterized with effective medium strips instead of an effective medium layer to account for the multilayer strips and the underlying periodic nature of the grating. This approach is convenient for describing such intermediate gratings for two types of applications: both metafilms and the coupling of incident waves to waveguide modes or diffraction orders. The parameters of the effective strips are retrieved by matching the spectral-angular map at different incident angles.

Large-scale nanoporous metal-coated silica aerogels for high SERS effect improvement.

We investigate the optical properties and surface-enhanced Raman scattering (SERS) characteristics of metal-coated silica aerogels. Silica aerogels were fabricated by easily scalable sol-gel and supercritical drying processes. Metallic nanogaps were formed on the top surface of the nanoporous silica network by controlling the thickness of the metal layer. The optimized metallic nanogap structure enabled strong confinement of light inside the gaps, which is a suitable property for SERS effect. We experimentally evaluated the SERS enhancement factor with the use of benzenethiol as a probe molecule. The enhancement factor reached 7.9 × 107 when molecules were adsorbed on the surface of the 30 nm silver-coated aerogel. We also theoretically investigated the electric field distribution dependence on the structural geometry and substrate indices. On the basis of FDTD simulations, we concluded that the electric field was highly amplified in the vicinity of the target analyte owing to a combination of the aerogel's ultralow refractive index and the high-density metallic nanogaps. The aerogel substrate with metallic nanogaps shows great potential for use as an inexpensive, highly sensitive SERS platform to detect environmental and biological target molecules.