The Interplay of Symmetry and Scattering Phase in Second Harmonic Generation from Gold Nanoantennas.

Nonlinear phenomena are central to modern photonics but, being inherently weak, typically require gradual accumulation over several millimeters. For example, second harmonic generation (SHG) is typically achieved in thick transparent nonlinear crystals by phase-matching energy exchange between light at initial, ω, and final, 2ω, frequencies. Recently, metamaterials imbued with artificial nonlinearity from their constituent nanoantennas have generated excitement by opening the possibility of wavelength-scale nonlinear optics. However, the selection rules of SHG typically prevent dipole emission from simple nanoantennas, which has led to much discussion concerning the best geometries, for example, those breaking centro-symmetry or incorporating resonances at multiple harmonics. In this work, we explore the use of both nanoantenna symmetry and multiple harmonics to control the strength, polarization and radiation pattern of SHG from a variety of antenna configurations incorporating simple resonant elements tuned to light at both ω and 2ω. We use a microscopic description of the scattering strength and phases of these constituent particles, determined by their relative positions, to accurately predict the SHG radiation observed in our experiments. We find that the 2ω particles radiate dipolar SHG by near-field coupling to the ω particle, which radiates SHG as a quadrupole. Consequently, strong linearly polarized dipolar SHG is only possible for noncentro-symmetric antennas that also minimize interference between their dipolar and quadrupolar responses. Metamaterials with such intra-antenna phase and polarization control could enable compact nonlinear photonic nanotechnologies.

Multiresonant broadband optical antennas as efficient tunable nanosources of second harmonic light.

We report the experimental realization of efficient tunable nanosources of second harmonic light with individual multiresonant log-periodic optical antennas. By designing the nanoantenna with a bandwidth of several octaves, simultaneous enhancement of fundamental and harmonic fields is observed over a broad range of frequencies, leading to a high second harmonic conversion efficiency, together with an effective second order susceptibility within the range of values provided by widespread inorganic crystals. Moreover, the geometrical configuration of the nanoantenna makes the generated second harmonic signal independent from the polarization of the fundamental excitation. These results open new possibilities for the development of efficient integrated nonlinear nanodevices with high frequency tunability.

Saturated excitation of fluorescence to quantify excitation enhancement in aperture antennas.

Fluorescence spectroscopy is widely used to probe the electromagnetic intensity amplification on optical antennas, yet measuring the excitation intensity amplification is a challenge, as the detected fluorescence signal is an intricate combination of excitation and emission. Here, we describe a novel approach to quantify the electromagnetic amplification in aperture antennas by taking advantage of the intrinsic non linear properties of the fluorescence process. Experimental measurements of the fundamental f and second harmonic 2f amplitudes of the fluorescence signal upon excitation modulation are used to quantify the electromagnetic intensity amplification with plasmonic aperture antennas.

Plasmonic antennas for directional sorting of fluorescence emission.

Spontaneous emission of fluorescent molecules or quantum dots is radiated along all directions when emitters are diluted in a liquid solution, which severely limits the amount of collected light. Besides, the emission direction does not carry any useful information and cannot be used to sort different molecules. To go beyond these limits, optical antennas have been recently introduced as conceptual tools to control the radiation properties for nanoemitters fixed on a substrate. Despite intense recent research, controlling the luminescence directivity remains a challenge for emitters with random positions and orientations, which is a key for several biomolecular screening applications. Here, we present full directional control of the fluorescence emission from molecules in water solution by an optical antenna made of a nanoaperture surrounded by a periodic set of shallow grooves in a gold film. For each emission wavelength, the fluorescence beam can be directed along a specific direction with a given angular width, hereby realizing a micrometer-size dispersive antenna. We demonstrate the fluorescence beaming results from an interference phenomenon and provide physical optics guidelines to control the fluorescence directivity by tuning the groove-nanoaperture distance. This photon-sorting capability provides a new approach for high-sensitivity screening of molecular species in solution.

Bright unidirectional fluorescence emission of molecules in a nanoaperture with plasmonic corrugations.

Controlling the fluorescence emission from nanoscale quantum emitters is a key element for a wide range of applications, from efficient analytical sensing to quantum information processing. Enhancing the fluorescence intensity and narrowing the emission directivity are both essential features to achieve a full control of fluorescence, yet this is rarely obtained simultaneously with optical nanoantennas. Here we report that gold nanoapertures surrounded by periodic corrugations transform standard fluorescent molecules into bright unidirectional sources. We obtain enhancement factors of the fluorescence count rate per molecule up to 120 fold simultaneously with a directional emission of the fluorescence into a narrow angular cone in the direction normal to the sample plane. The bright emission and narrow directionality enable the detection of single molecules with a low numerical aperture objective, and improve the effectiveness of fluorescence-based applications. We thoroughly quantify the increased light-matter coupling as well as the radiation pattern intensity. These results are highly relevant for the development of single molecule sensing, single-photon sources, and light emitting devices.

Large molecular fluorescence enhancement by a nanoaperture with plasmonic corrugations.

We investigate the influence of circular corrugations surrounding a central nanoaperture to further enhance the fluorescence count rate per emitter and control its emission directionality. Adding a single corrugation already allows to significantly increase the fluorescence signal as compared to a bare nanoaperture. A complete fluorescence characterization quantifies the excitation and emission gains contributing to the fluorescence enhancement process as the number of corrugations is increased.

Deciphering fluorescence signals by quantifying separately the excitation intensity from the number of emitters.

Conventional fluorescence detection is sensitive to an intricate product of the number of fluorescent emitters times the local excitation intensity. Here, we describe a method to locally quantify the excitation intensity and the number of emitters separately, enabling a clear distinction between the phenomena responsible for a given fluorescence signal. Our technique is based on harmonic excitation modulation and higher-order fluorescence demodulation. It is compatible with a wide range of observations, opening new characterization routes for fluorescence detection or imaging on complex systems, such as plasmonic substrates or scattering media.

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.

Optical-fiber-microsphere for remote fluorescence correlation spectroscopy.

Fluorescence correlation spectroscopy (FCS) is a versatile method that would greatly benefit to remote optical-fiber fluorescence sensors. However, the current state-of-the-art struggles with high background and low detection sensitivities that prevent the extension of fiber-based FCS down to the single-molecule level. Here we report the use of an optical fiber combined with a latex microsphere to perform FCS analysis. The sensitivity of the technique is demonstrated at the single molecule level thanks to a photonic nanojet effect. This offers new opportunities for reducing the bulky microscope setup and extending FCS to remote or in vivo applications.

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.

Third-harmonic-upconversion enhancement from a single semiconductor nanoparticle coupled to a plasmonic antenna.

The ability to convert low-energy quanta into a quantum of higher energy is of great interest for a variety of applications, including bioimaging, drug delivery and photovoltaics. Although high conversion efficiencies can be achieved using macroscopic nonlinear crystals, upconverting light at the nanometre scale remains challenging because the subwavelength scale of materials prevents the exploitation of phase-matching processes. Light-plasmon interactions that occur in nanostructured noble metals have offered alternative opportunities for nonlinear upconversion of infrared light, but conversion efficiency rates remain extremely low due to the weak penetration of the exciting fields into the metal. Here, we show that third-harmonic generation from an individual semiconductor indium tin oxide nanoparticle is significantly enhanced when coupled within a plasmonic gold dimer. The plasmonic dimer acts as a receiving optical antenna, confining the incident far-field radiation into a near field localized at its gap; the indium tin oxide nanoparticle located at the plasmonic dimer gap acts as a localized nonlinear transmitter upconverting three incident photons at frequency ω into a photon at frequency 3ω. This hybrid nanodevice provides third-harmonic-generation enhancements of up to 10(6)-fold compared with an isolated indium tin oxide nanoparticle, with an effective third-order susceptibility up to 3.5 × 10(3) nm V(-2) and conversion efficiency of 0.0007%. We also show that the upconverted third-harmonic emission can be exploited to probe the near-field intensity at the plasmonic dimer gap.

Ultrasensitive broadband probing of molecular vibrational modes with multifrequency optical antennas.

Optical antennas represent an enabling technology for enhancing the detection of molecular vibrational signatures at low concentrations and probing the chemical composition of a sample in order to identify target molecules. However, efficiently detecting different vibrational modes to determine the presence (or the absence) of a molecular species requires a multispectral interrogation in a window of several micrometers, as many molecules present informative fingerprint spectra in the mid-infrared between 2.5 and 10 µm. As most nanoantennas exhibit a narrow-band response because of their dipolar nature, they are not suitable for such applications. Here, we propose the use of multifrequency optical antennas designed for operating with a bandwidth of several octaves. We demonstrate that surface-enhanced infrared absorption gains in the order of 10(5) can be easily obtained in a spectral window of 3 µm with attomolar concentrations of molecules, providing new opportunities for ultrasensitive broadband detection of molecular species via vibrational spectroscopy techniques.

Two-photon fluorescence correlation spectroscopy with high count rates and low background using dielectric microspheres.

Two-photon excitation fluorescence is a powerful technique commonly used for biological imaging. However, the low absorption cross section of this non-linear process is a critical issue for performing biomolecular spectroscopy at the single molecule level. Enhancing the two-photon fluorescence signal would greatly improve the effectiveness of this technique, yet current methods struggle with medium enhancement factors and/or high background noise. Here, we show that the two-photon fluorescence signal from single Alexa Fluor 488 molecules can be enhanced up to 10 times by using a 3 µm diameter latex sphere while adding almost no photoluminescence background. We report a full characterization of the two-photon fluorescence enhancement by a single microsphere using fluorescence correlation spectroscopy. This opens new routes to enhance non-linear optical signals and extend biophotonic applications.

Colloidal quantum dots as probes of excitation field enhancement in photonic antennas.

Optical antennas are essential devices to interface light to nanoscale volumes and locally enhance the electromagnetic intensity. Various experimental methods can be used to quantify the antenna amplification on the emission process, yet characterizing the antenna amplification at the excitation frequency solely is a challenging task. Such experimental characterization is highly needed to fully understand and optimize the antenna response. Here, we describe a novel experimental tool to directly measure the antenna amplification on the excitation field independently of the emission process. We monitor the transient emission dynamics of colloidal quantum dots and show that the ratio of doubly to singly excited state photoluminescence decay amplitudes is an accurate tool to quantify the local excitation intensity amplification. This effect is demonstrated on optical antennas made of polystyrene microspheres and gold nanoapertures, and supported by numerical computations. The increased doubly excited state formation on nanoantennas realizes a new demonstration of enhanced light-matter interaction at the nanoscale.

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.