Tailoring Experimental Configurations to Probe Transition Dipoles of Fluorescent Nanoemitters by Polarimetry or Fourier Imaging with Enhanced Sensitivity.

Probing the transition dipoles responsible for the luminescence of a nanoemitter is essential to understanding its physical properties, its interactions with its environment, and its potential applications. Various methods in photoluminescence microscopy, based on polarimetry or Fourier imaging, have been developed to measure an emitter's dipole properties: the number of radiating dipoles, the oscillator strength ratio between them, and their orientation. In this article, we model the most used of these protocols and show that their sensitivity depends crucially on the experimental conditions: substrate material, presence of another lower or upper layer, and objective numerical aperture. We develop guidelines to optimize the measurement sensitivity by tailoring the experimental conditions, depending on the type of protocol used and the dipole property to be measured.

Enhancing Magnetic Light Emission with All-Dielectric Optical Nanoantennas.

Electric and magnetic optical fields carry the same amount of energy. Nevertheless, the efficiency with which matter interacts with electric optical fields is commonly accepted to be at least 4 orders of magnitude higher than with magnetic optical fields. Here, we experimentally demonstrate that properly designed photonic nanoantennas can selectively manipulate the magnetic versus electric emission of luminescent nanocrystals. In particular, we show selective enhancement of magnetic emission from trivalent europium-doped nanoparticles in the vicinity of a nanoantenna tailored to exhibit a magnetic resonance. Specifically, by controlling the spatial coupling between emitters and an individual nanoresonator located at the edge of a near-field optical scanning tip, we record with nanoscale precision local distributions of both magnetic and electric radiative local densities of states (LDOS). The map of the radiative LDOS reveals the modification of both the magnetic and electric quantum environments induced by the presence of the nanoantenna. This manipulation and enhancement of magnetic light-matter interaction by means of nanoantennas opens up new possibilities for the research fields of optoelectronics, chiral optics, nonlinear and nano-optics, spintronics, and metamaterials, among others.

Rats can acquire conditional fear of faint light leaking through the acrylic resin used to mount fiber optic cannulas.

Rodents are exquisitely sensitive to light and optogenetic behavioral experiments routinely introduce light-delivery materials into experimental situations, which raises the possibility that light could leak and influence behavioral performance. We examined whether rats respond to a faint diffusion of light, termed caplight, which emanated through the translucent dental acrylic resin used to affix deep-brain optical cannulas in place. Although rats did not display significant changes in locomotion or rearing to caplight in a darkened open field, they did acquire conditional fear via caplight-footshock pairings. These findings highlight the potential confounding influence of extraneous light emanating from light-delivery materials during optogenetic analyses.

Imprinted Photonic Hydrogels for the Size- and Shell-Selective Recognition of Nanoparticles.

Sensors based on responsive photonic hydrogels have recently attracted considerable attention for visual medical diagnostics, pharmaceutical bioassays, and environmental monitoring. However, the use of these promising materials for the detection of nanoparticles (NPs) has never been explored so far, although the sensing of nanoobjects is a rapidly evolving area of research. To address this issue, we have combined the concepts of inverse-opal hydrogels and nanoparticle-imprinted polymers. In this way, we could obtain a NP-imprinted photonic hydrogel consisting of a three-dimensional, highly ordered poly(methacrylic acid) macroporous array, in which nanocavities complementary to the target NPs, in this case colloidal quantum dots, are distributed. This novel type of NP-imprinted photonic hydrogel sensor was shown to display high sensitivity and selectivity, thus opening new prospects for the development of equipment-free and cost-efficient sensing devices for NPs.

Near-field to far-field characterization of speckle patterns generated by disordered nanomaterials.

We study the intensity spatial correlation function of optical speckle patterns above a disordered dielectric medium in the multiple scattering regime. The intensity distributions are recorded by scanning near-field optical microscopy (SNOM) with sub-wavelength spatial resolution at variable distances from the surface in a range which spans continuously from the near-field (distance ≪ λ) to the far-field regime (distance ≫ λ). The non-universal behavior at sub-wavelength distances reveals the connection between the near-field speckle pattern and the internal structure of the medium.

Inverse opals of molecularly imprinted hydrogels for the detection of bisphenol A and pH sensing.

Inverse opal films of molecularly imprinted polymers (MIP) were elaborated using the colloidal crystal template method. The colloidal crystals of silica particles were built by the Langmuir-Blodgett technique, allowing a perfect control of the film thickness. Polymerization in the interspaces of the colloidal crystal in the presence of bisphenol A (BPA) and removal of the used template provides 3D-ordered macroporous methacrylic acid-based hydrogel films in which nanocavities derived from bisphenol A are distributed within the thin walls of the inverse opal hydrogel. The equilibrium swelling properties of the nonimprinted (NIPs) and molecularly imprinted polymers (MIPs) were studied as a function of pH and bisphenol A concentration, while the molecular structures of the bulk hydrogels were analyzed using a cross-linked network structure theory. This study showed an increase in nanopore (mesh) size in the MIPs after BPA extraction as compared to NIPs, in agreement with the presence of nanocavities left by the molecular imprints of the template molecule. The resulting inverse opals were found to display large responses to external stimuli (pH or BPA) with Bragg diffraction peak shifts depending upon the hydrogel film thickness. The film thickness was therefore shown to be a critical parameter for improving the sensing capacities of inverse opal hydrogel films deposited on a substrate.

Fabrication of Efficient Single-Emitter Plasmonic Patch Antennas by Deterministic In Situ Optical Lithography using Spatially Modulated Light.

Single-emitter plasmonic patch antennas are room-temperature deterministic single-photon sources, which exhibit highly accelerated and directed single-photon emission. However, for efficient operation these structures require 3D nanoscale deterministic control of emitter positioning within the device, which is a demanding task, especially when emitter damage during fabrication is a major concern. To overcome this limitation, the deterministic room-temperature in situ optical lithography protocol uses spatially modulated light to position a plasmonic structure nondestructively on any selected single-emitter with 3D nanoscale control. Herein, the emission statistics of such plasmonic antennas that embed a deterministically positioned single colloidal CdSe/CdS quantum dot, which highlight acceleration and brightness of emission, are analyzed. It is demonstrated that the presented antenna induces a 1000-fold effective increase in the absorption cross-section, and, under high pumping, these antennas show nonlinearly enhanced emission.

Tesla-Range Femtosecond Pulses of Stationary Magnetic Field, Optically Generated at the Nanoscale in a Plasmonic Antenna.

The inverse Faraday effect allows the generation of stationary magnetic fields through optical excitation only. This light-matter interaction in metals results from creating drift currents via nonlinear forces that light applies to the conduction electrons. Here, we describe the theory underlying the generation of drift currents in metals, particularly its application to photonic nanostructures using numerical simulations. We demonstrate that a gold photonic nanoantenna, optimized by a genetic algorithm, allows, under high excitation power, to maximize the drift currents and generate a pulse of stationary magnetic fields in the tesla range. This intense magnetic field, confined at the nanoscale and for a few femtoseconds, results from annular optical confinement and not from the creation of a single optical hot spot. Moreover, by controlling the incident polarization state, we demonstrate the orientation control of the created magnetic field and its reversal on demand. Finally, the stationary magnetic field's temporal behavior and the drift currents associated with it reveal the subcycle nature of this light-matter interaction. The manipulation of drift currents by a plasmonic nanostructure for the generation of stationary magnetic field pulses finds applications in the ultrafast control of magnetic domains with applications not only in data storage technologies but also in research fields such as magnetic trapping, magnetic skyrmion, magnetic circular dichroism, to spin control, spin precession, spin currents, and spin-waves, among others.

Isotropic broadband absorption by a macroscopic self-organized plasmonic crystal.

We describe the plasmonic properties of a two-dimensional periodic metallic grating of macroscopic size obtained by gold deposition on a self-assembled silica opal. Structural characterization shows a transition from microscopic order to isotropy at macroscopic scale. Optical reflection spectra exhibit a dip of almost complete absorption due to coupling to surface-plasmon-polaritons (SPP). This is explained by theoretical calculations introducing a density of coupled SPP modes. We demonstrate, at a given incidence angle, a broad continuum of coupled wavelengths over the visible spectrum. This opens new possibilities in fields where light-plasmon coupling is required over a broad range of wavelengths and incidence orientations.

Experimental measurement of local high temperature at the surface of gold nanorods using doped ZnGa2O4 as a nanothermometer.

Heat measurement induced by photoexcitation of a plasmonic metal nanoparticle assembly under environmental conditions is of primary importance for the further development of applications in the fields of (photo)catalysis, nanoelectronics and nanomedicine. Nevertheless, the fine control of the rise in temperature remains difficult and limits the use of this technology due to the lack of local temperature measurement tools working under environmental conditions. Luminescence nanothermometers are an alternative solution to the limitations of conventional contact thermometers since they are able to give an absolute temperature value with high spatial resolution using common optical equipment. As a proof of concept of this nanothermometry approach, a high local temperature exceeding one hundred degrees is measured on the thermalized photoexcited aggregate of gold nanorods using ZnGa2O4:Cr3+,Bi3+ nanothermometers that have a strong temperature dependence on the luminescence lifetime of chromium(iii) and high sensitivity over an extensive range of temperatures. A study on the influence of the average distance between nanosensors and nanoheaters on the measured temperature is carried out by coating the nanosensors with a silica layer of tunable thickness, highlighting the temperature gradient at the vicinity of the nanoheater as the theory predicts. The variation of the optical nanosensor response is relevant and promising, and it could be further envisioned as a potential candidate for local temperature measurement at the nanoscale since no plasmonic effect on Cr3+ lifetime is observed. The results reported here open up an even wider field of application for high temperature nanothermometry on real samples such as aggregate particles for many applications including catalysis and nanoelectronics. Thermometry using luminescent nanoprobes, which is complementary to thermal microscopy techniques, will allow in situ and in operando temperature monitoring at very small scales.

Single Gold Bipyramid Nanoparticle Orientation Measured by Plasmon-Resonant Scattering Polarimetry.

The 3D orientation of a single gold nanoparticle is probed experimentally by light scattering polarimetry. We choose high-quality gold bipyramids (AuBPs) that support around 700 nm a well-defined narrow longitudinal localized surface plasmonic resonance (LSPR) which can be considered as a linear radiating dipole. A specific spectroscopic dark-field technique was used to control the collection angles of the scattered light. The in-plane as well as the out-of-plane angles are determined by analyzing the polarization of the scattered radiation. The data are compared with a previously developed model where the environment and the angular collection both play crucial roles. We show that most of the single AuBPs present an out-of-plane orientation consistent with their geometry. Finally, the fundamental role of the collection angles on the determination of the orientation is investigated for the first time. Several features are then deduced: we validate the choice of the analytical 1D model, an accurate 3D orientation is obtained, and the critical contribution of the evanescent waves is highlighted.

Frequency doubling of low power images using a self-imaging cavity.

A self-imaging resonator can be simultaneously resonant for many transverse modes and therefore allows cavity build-up for images of various shapes. The stability properties of such a cavity are reviewed. We have used this device for the first time to enhance the efficiency of second harmonic generation of weak images. We characterize the global and local efficiency of the second harmonic generation, and discuss its limitation due to the spatial bandwidth of the cavity and the diffraction along the crystal length.

Controlled modification of single colloidal CdSe/ZnS nanocrystal fluorescence through interactions with a gold surface.

Single colloidal CdSe/ZnS nanocrystals are deposited at various distances from a gold film in order to improve their performance as single photon sources. Photon antibunching is demonstrated and the experimental curves are accurately fitted by theoretical equations. Emission lifetime and intensity are measured and found in excellent agreement with theoretical values. The various effects of a neighbouring gold film are discussed : interferences of the excitation beam, interferences of the fluorescence light, opening of plasmon and lossy-surface-wave modes, modification of the radiation pattern leading to a modified objective collection efficiency. At 80 nm from the gold film, when using an objective with 0.75 numerical aperture, about a 2.4-fold increase of the detected intensity is evidenced.

Thermoresponsive colloidal crystals built from core-shell poly(styrene/alpha-tert-butoxy-omega-vinylbenzylpolyglycidol) microspheres.

Core-shell particles of poly(styrene/alpha-tert-butoxy-omega-vinylbenzylpolyglycidol) P(S/PGL) were used as new building blocks for the assembly of a colloidal crystal. The added-value properties of these particles for photonic crystal architectures are their high hydrophilicity together with their thermoresponsivity. Indeed, the poglycidol-rich shell undergoes a phase transition above 45 degrees C, which leads to its collapse at the particle surface accompanied by a decrease in the particle diameter. The three-dimensional crystalline arrays display Bragg diffraction properties, as judged by angle-resolved reflectance spectroscopy. The thermoresponsivity of the colloidal assemblies was observed through modifications of their optical properties with respect to the temperature used during the assembly process. The wetting properties of the crystalline material were also shown to reversibly switch from hydrophilic to hydrophobic as a function of the assembly temperature, thus evidencing the reorganization of the surface polyglycidol chains during the polymer phase transition. This work shows conclusively that P(S/PGL) particles are promising alternatives to poly(N-isopropylacrylamide) and poly(ethylene glycol) particles for the elaboration of thermoresponsive colloidal crystals, with a phase transition situated in between those of these two polymers.

Fine tuning of emission through the engineering of colloidal crystals.

We describe the preparation and characterization of photonic colloidal crystals from silica spheres with incorporated luminescent [Mo(6)Br(14)](2-) cluster units. These structures exhibit strong angle-dependent luminescent properties. The incorporation of one or several planar defects in the periodic structures gives rise to the creation of a passband in the stopband. In the energy range of this passband, an increase of the emission intensity has been found.

Extreme multiexciton emission from deterministically assembled single-emitter subwavelength plasmonic patch antennas.

Coupling nano-emitters to plasmonic antennas is a key milestone for the development of nanoscale quantum light sources. One challenge, however, is the precise nanoscale positioning of the emitter in the structure. Here, we present a laser etching protocol that deterministically positions a single colloidal CdSe/CdS core/shell quantum dot emitter inside a subwavelength plasmonic patch antenna with three-dimensional nanoscale control. By exploiting the properties of metal-insulator-metal structures at the nanoscale, the fabricated single-emitter antenna exhibits a very high-Purcell factor (>72) and a brightness enhancement of a factor of 70. Due to the unprecedented quenching of Auger processes and the strong acceleration of the multiexciton emission, more than 4 photons per pulse can be emitted by a single quantum dot, thus increasing the device yield. Our technology can be applied to a wide range of photonic nanostructures and emitters, paving the way for scalable and reliable fabrication of ultra-compact light sources.

Introduction of a planar defect in a molecularly imprinted photonic crystal sensor for the detection of bisphenol A.

This paper reports the preparation of a molecularly imprinted inverse opal hydrogel containing a 2D defect layer, by combining the Langmuir-Blodgett technique and the photonic crystal template method. By coupling the exceptional characteristics of molecularly imprinted polymers, sensitive to the presence of a target molecule, and those of photonic crystals in a single device, we could obtain a defect-embedded imprinted photonic polymer consisting in a three-dimensional, highly-ordered and interconnected macroporous array, where nanocavities complementary to analytes in shape and binding sites are distributed. As a proof of concept, we prepared a three-dimensional macroporous array of poly(methacrylic acid) (PMAA) containing molecular imprints of bisphenol A (BPA) and a planar defect layer consisting in macropores of different size. The optical properties of the resulting inverse opal were investigated using reflection spectroscopy. The defect layer was shown to enhance the sensitivity of the photonic crystal material, opening new possibilities towards the development smart optical sensing devices.

Experimental Determination of the Fluorescence Quantum Yield of Semiconductor Nanocrystals.

Many studies have considered the luminescence of colloidal II-VI nanocrystals, both in solution at a collective scale and at an individual scale by confocal microscopy. The quantum yield is an important figure of merit for the optical quality of a fluorophore. We detail here a simple method to determine the quantum yield of nanocrystals in solution as a function of the absorption. For this purpose, we choose rhodamine 101 as a reference dye to measure the nanocrystal fluorescence quantum yield. The influence of the concentration on quantum yield is therefore studied for both the reference and the solutions of nanocrystals and is found to be critical for the acuity of the method. Different types of nanocrystals are studied to illustrate different quantum yield evolutions with the concentration.