Decoding Polarization in a Single Achiral Gold Nanostructure from Emitted Far-Field Radiation.

The emergence of optical chirality in the light emitted from plasmonic nanostructures is commonly associated with their geometrical chirality. Although it has been demonstrated that even achiral structures can exhibit chiral near-fields, the existence of chiroptical far-field responses of such structures is widely neglected. In this paper, we present a detailed analysis of the polarization state in a single planar achiral plasmonic nanostructure that sustains more than one prominent plasmon mode. In consideration of the relative phase, the superposition of the fields associated with these modes determines the polarization state of the emitted light in the far-field. Supported by simulations of the surface charge distribution of the particle, we show that the polarization state of the emitted light is already determined in the near-field. The chiroptical far-field responses are analyzed by polarized single-particle dark-field scattering spectroscopy. We introduce an analytical model that enables us to obtain the polarization information from the spectra of structures with dipolar resonances taken under unpolarized illumination. The same principle is confirmed in polarimetric spectroscopy measurements on rhomboids with systematically varied angles, therefore, introducing increasing values of geometrical chirality to the structures. The agreement between the calculation and measurement demonstrates the general validity of our model for both chiral and achiral structures.

Electrically switchable structural colors based on liquid-crystal-overlaid aluminum anisotropic nanoaperture arrays.

Actively tunable or reconfigurable structural colors are highly promising in future development for high resolution imaging and displaying applications. To this end, we demonstrate switchable structural colors covering the entire visible range by integrating aluminum nanoaperture arrays with nematic liquid crystals. The geometrically anisotropic design of the nanoapertures provides strong polarization-dependent coloration. By overlaying a nematic liquid crystal layer, we further demonstrate switchable ability of the structural colors by either changing the polarization of the incident light or applying an external voltage. The switchable structural colors have a fast response time of 28 ms at a driving voltage of 6.5 V. Furthermore, colorful patterns are demonstrated by coding the colors with various dimensions of nanoaperture arrays with dual switching modes. Our proposed technique in this work provides a dual-mode switchable structural colors, which is highly promising for polarimetric displays, imaging sensors, and visual cryptography.

Aluminum Cayley trees as scalable, broadband, multiresonant optical antennas.

An optical antenna can convert a propagative optical radiation into a localized excitation and the reciprocal. Although optical antennas can be readily created using resonant nanoparticles (metallic or dielectric) as elementary building blocks, the realization of antennas sustaining multiple resonances over a broad range of frequencies remains a challenging task. Here, we use aluminum self-similar, fractal-like structures as broadband optical antennas. Using electron energy loss spectroscopy, we experimentally evidence that a single aluminum Cayley tree, a simple self-similar structure, sustains multiple plasmonic resonances. The spectral position of these resonances is scalable over a broad spectral range spanning two decades, from ultraviolet to midinfrared. Such multiresonant structures are highly desirable for applications ranging from nonlinear optics to light harvesting and photodetection, as well as surface-enhanced infrared absorption spectroscopy.

Electrically Switchable, Polarization-Sensitive Encryption Based on Aluminum Nanoaperture Arrays Integrated with Polymer-Dispersed Liquid Crystals.

Metasurface-based structural coloration is a promising enabling technology for advanced optical encryption with a high-security level. Herein, we propose a paradigm of electrically switchable, polarization-sensitive optical encryption based on designed metasurfaces integrated with polymer-dispersed liquid crystals. The metasurfaces consist of anisotropic and isotropic aluminum nanoaperture arrays. Optical images can be encrypted by elaborately arranging anisotropic and isotropic nanoapertures based on their polarization-dependent plasmonic resonance characteristics. We demonstrate high-quality encrypted images and QR codes with electrically switchable, polarization-sensitive properties based on PDLC-integrated aluminum nanoaperture arrays. The proposed technique can be applied to many fields including high-security optical encryption, security tags, anticounterfeiting, multichannel imaging, and dynamic displays.

Surface roughness and substrate induced symmetry-breaking: influence on the plasmonic properties of aluminum nanostructure arrays.

The surface topography is known to play an important role on the near- and far-field optical properties of metallic nanoparticles. In particular, aluminum (Al) nanoparticles are commonly fabricated through evaporation techniques, therefore exhibiting elevated surface roughness additionally to their native oxide layer. In this study, the mode-dependent influence of surface roughness on the plasmonic properties sustained by Al nanodisks (NDs) is first numerically investigated using a realistic model taking into account the thin native oxide layer. Due to the symmetry-breaking induced by the supporting dielectric substrate to Al ND, it appears that the roughness affects differently the substrate-induced out-of-plane quadrupolar mode (below 300 nm) and the in-plane dipolar mode sustained by the Al ND. By increasing the top surface roughness of the Al ND, the substrate-induced quadrupolar mode is significantly damped especially in the ultraviolet regime, while the dipolar resonance is broadened and redshifted. The explanation of these effects relies in the decoherence and dissipation of the collective electronic oscillations as a result of the top surface roughness to the different near-field distribution of the out-of-plane quadrupolar mode and in-plane dipolar mode. Moreover, the influences of the diameter of Al ND, dielectric substrate with different refractive index, and the oxidation of Al ND on these two modes are also investigated. Particularly, the quadrupolar mode disappears with surface roughness and oxidation, explaining why this mode is very weak and sometimes barely visible on evaporated Al nanostructures reported in the literature. Finally, these results are experimentally confirmed by characterizing the optical properties of periodic Al ND arrays.

Hybrid nanostructured plasmonic electrodes for flexible organic light-emitting diodes.

Improved performance in flexible organic light-emitting diodes (OLEDs) is demonstrated by using a hybrid nanostructured plasmonic electrode consisting of silver nanowires (AgNWs) decorated with silver nanoparticles (AgNPs) and covered by exfoliated graphene sheets. Such all-solution processed electrodes show high optical transparency and electrical conductivity. When integrated in an OLED with super yellow polyphenylene vinylene as the emissive layer, the plasmon coupling of the NW-NP hybrid plasmonic system is found to significantly enhance the fluorescence, demonstrated by both simulations and photoluminescence measurements, leading to a current efficiency of 11.61 cd A-1 and a maximum luminance of 20 008 cd m-2 in OLEDs. Stress studies reveal a superior mechanical flexibility to the commercial indium-tin-oxide (ITO) counterparts, due to the incorporation of exfoliated graphene sheets. Our results show that these hybrid nanostructured plasmonic electrodes can be applied as an effective alternative to ITO for use in high-performance flexible OLEDs.

Local Optical Chirality Induced by Near-Field Mode Interference in Achiral Plasmonic Metamolecules.

When circularly polarized light interacts with a nanostructure, the optical response depends on the geometry of the structure. If the nanostructure is chiral (i.e., it cannot be superimposed on its mirror image), then its optical response, both in near-field and far-field, depends on the handedness of the incident light. In contrast, achiral structures exhibit identical far-field responses for left- and right-circular polarization. Here, we show that a perfectly achiral nanostructure, a plasmonic metamolecule with trigonal D3h symmetry, exhibits a near-field response that is sensitive to the handedness of light. This effect stems from the near-field interference between the different plasmonic modes sustained by the plasmonic metamolecule under circularly polarized light excitation. The local chirality in a plasmonic trimer is then experimentally evidenced with nanoscale resolution using a molecular probe. Our experiments demonstrate that the optical near-field chirality can be imprinted into the photosensitive polymer, turning an optical chirality into a geometrical chirality that can be imaged using atomic force microscopy. These results are of interest for the field of polarization-sensitive photochemistry.

Detecting a Zeptogram of Pyridine with a Hybrid Plasmonic-Photonic Nanosensor.

Thanks to their small sensing volume, nanosensors based on localized surface plasmon resonances (LSPR) allow the detection of minute amounts of analytes, down to the single-molecule limit. However, the detected analytes are often large molecules, such as proteins. The detection of small molecules remains largely unexplored. Here, we use a hybrid photonic-plasmonic nanosensor to detect a small target molecule (pyridine). The sensor's design is based on a dielectric photonic microstructure acting as an antenna, which efficiently funnels light toward a plasmonic transducer and enhances the detection efficiency. This sensor exhibits a limit of detection as small as 10-14 mol L-1. Using a calibration procedure based on electrodynamical numerical simulations, we compute the number of detected molecules. This yields a limit of detection in mass of 4 zeptograms (1 zg = 10-21 g), a record value for plasmonic molecular sensors. Our system can hence be seen as an optical molecular weighing scale, enabling room temperature detection of mass at the zeptogram scale.

High-resolution imaging and spectroscopy of multipolar plasmonic resonances in aluminum nanoantennas.

We report on the high resolution imaging of multipolar plasmonic resonances in aluminum nanoantennas using electron energy loss spectroscopy (EELS). Plasmonic resonances ranging from near-infrared to ultraviolet (UV) are measured. The spatial distributions of the multipolar resonant modes are mapped and their energy dispersion is retrieved. The losses in the aluminum antennas are studied through the full width at half-maximum of the resonances, unveiling the weight of both interband and radiative damping mechanisms of the different multipolar resonances. In the blue-UV spectral range, high order resonant modes present a quality factor up to 8, two times higher than low order resonant modes at the same energy. This study demonstrates that near-infrared to ultraviolet tunable multipolar plasmonic resonances in aluminum nanoantennas with relatively high quality factors can be engineered. Aluminum nanoantennas are thus an appealing alternative to gold or silver ones in the visible and can be efficiently used for UV plasmonics.

Plasmonic engineering of spontaneous emission from silicon nanocrystals.

Silicon nanocrystals offer huge advantages compared to other semi-conductor quantum dots as they are made from an abundant, non-toxic material and are compatible with silicon devices. Besides, among a wealth of extraordinary properties ranging from catalysis to nanomedicine, metal nanoparticles are known to increase the radiative emission rate of semiconductor quantum dots. Here, we use gold nanoparticles to accelerate the emission of silicon nanocrystals. The resulting integrated hybrid emitter is 5-fold brighter than bare silicon nanocrystals. We also propose an in-depth analysis highlighting the role of the different physical parameters in the photoluminescence enhancement phenomenon. This result has important implications for the practical use of silicon nanocrystals in optoelectronic devices, for instance for the design of efficient down-shifting devices that could be integrated within future silicon solar cells.

Intense Bessel-like beams arising from pyramid-shaped microtips.

We show both numerically and experimentally that intense, narrow, and low-divergence beams of light are produced at the apex of dielectric pyramid-shaped microtips. These beams exhibit a Bessel transverse profile but are narrower than the usual Bessel beam, allowing for a significant enhancement of the light intensity inside the beam. They are generated by axicon-like structures with submicrometric height imprinted in glass by combining optical lithography and chemical etching. The resulting beams are experimentally imaged using fluorescence microscopy, in remarkable agreement with numerical computations.

Off-Resonant Optical Excitation of Gold Nanorods: Nanoscale Imprint of Polarization Surface Charge Distribution.

We report on the nanoscale optical characterization of gold nanorods irradiated out of their plasmonic resonance. Our approach is based on the reticulation of a photopolymerizable formulation locally triggered by enhanced electromagnetic fields. The tiny local field enhancement stems from the surface polarization charges associated with the electric field discontinuity at the metal/dielectric interface. This allows us to get a nanoscale signature of the spatial distribution of the surface charge density in metallic nanoparticles irradiated off-resonance.

Crucial role of the adhesion layer on the plasmonic fluorescence enhancement.

A nanoscale layer of chromium or titanium is commonly used in plasmonic nanoantennas to firmly adhere a gold film to a glass substrate, yet the influence of this layer on the antenna performance is often ignored. As a result, the need for the use of potentially better materials is not widely recognized. Using a single aperture milled in a gold film with 120 nm diameter as a nanobench for these investigations, we present the first experimental report of the strong dependence of the plasmonic enhancement of single-molecule fluorescence on the nature of the adhesion layer. By combining fluorescence correlation spectroscopy and fluorescence lifetime measurements, we show that this structure is very sensitive to the properties of the adhesion layer, and we detail the respective contributions of excitation and emission gains to the observed enhanced fluorescence. Any increase in the absorption losses due to the adhesion layer permittivity or thickness is shown to lower the gains in both excitation and emission, which we relate to a damping of the energy coupling at the nanoaperture. With this nanobench, we demonstrate the largest enhancement factor reported to date (25×) by using a TiO(2) adhesion layer. The experimental data are supported by numerical simulations and argue for a careful consideration of the adhesion layer while designing nanoantennas for high-efficiency single-molecule analysis.

Three-dimensional subwavelength confinement of light with dielectric microspheres.

Dielectric microspheres are shown to be capable of confining light in a three-dimensional region of subwavelength dimensions when they are illuminated by tightly focused Gaussian beams. We show that a simple configuration, not involving resonances, permits one to reach an effective volume as small as 0.6 (lambda/n)(3). It is shown that this three-dimensional confinement arises from interferences between the field scattered by the sphere and the incident Gaussian beam containing high angular components.

Nanoaperture-enhanced signal-to-noise ratio in fluorescence correlation spectroscopy.

The fluorescence enhancement found in gold nanoapertures is demonstrated to increase the signal-to-noise ratio (SNR) in fluorescence correlation spectroscopy (FCS). Starting from a general discussion on noise in FCS experiments, we show that fluorescence enhancement leads to a dramatic increase in the SNR. This prediction is confirmed by experiments where we report an experimental gain in SNR of about 1 order of magnitude, corresponding to a 100-fold reduction of the experiment duration. This technique is then applied to monitor the kinetics of a fast enzymatic cleavage reaction. This set of experiments evidence the feasibility of FCS analysis with fast integration times of about 1 s, opening the way to the monitoring of a variety of biochemical reactions at reduced time scales.

Strong electromagnetic confinement near dielectric microspheres to enhance single-molecule fluorescence.

Latex microspheres are used as a simple and low-cost means to achieve three axis electromagnetic confinement below the standard diffraction limit. We demonstrate their use to enhance the fluorescence fluctuation detection of single molecules. Compared to confocal microscopy with high numerical aperture, we monitor a detection volume reduction of one order of magnitude below the diffraction limit together with a 5-fold gain in the fluorescence rate per molecule. This offers new opportunities for a broad range of applications in biophotonics, plasmonics, optical data storage and ultramicroscopy.

Disposable microscope objective lenses for fluorescence correlation spectroscopy using latex microspheres.

We explore the combination of a latex microsphere with a low NA lens to form a high performance optical system, and enable the detection of single molecules by fluorescence correlation spectroscopy (FCS). Viable FCS experiments at concentrations 1-1000 nM with different objectives costing less than $40 are demonstrated. This offers a simple and low-cost alternative to the conventional complex microscope objectives.

Field enhancement in a circular aperture surrounded by a single channel groove.

Numerical analysis of diffraction by a single aperture surrounded by a circular shallow channel in a metallic screen shows the possibility of a 50-fold increase of the electric field intensity inside the central aperture, when compared to the incident field. Detailed analysis of cavity modes and their coupling through surface plasmon wave determine the parameters leading to maximum field enhancement. This effect can be used in high-efficiency single-molecule fluorescence analysis in attoliter volumes.

Emission and excitation contributions to enhanced single molecule fluorescence by gold nanometric apertures.

We detail the role of single nanometric apertures milled in a gold film to enhance the fluorescence emission of Alexa Fluor 647 molecules. Combining fluorescence correlation spectroscopy and lifetime measurements, we determine the respective contributions of excitation and emission in the observed enhanced fluorescence. We characterize a broad range of nanoaperture diameters from 80 to 310 nm, and highlight the link between the fluorescence enhancement and the local photonic density of states. These results are of great interest to increase the effectiveness of fluorescence-based single molecule detection and to understand the interaction between a quantum emitter and a nanometric metal structure.

Near-field observation of subwavelength confinement of photoluminescence by a photonic crystal microcavity.

We present a direct, room-temperature near-field optical study of light confinement by a subwavelength defect microcavity in a photonic crystal slab containing quantum-well sources. The observations are compared with three-dimensional finite-difference time-domain calculations, and excellent agreement is found. Moreover, we use a subwavelength cavity to study the influence of a near-field probe on the imaging of localized optical modes.