Sébastien Bidault

Plasmon-Based Nanolenses Assembled on a Well-Defined DNA Template

The controlled and reproducible synthesis of closely spaced noble metal nanoparticle groupings is an essential step toward the rational design of nanostructures for surface enhanced Raman scattering with single-molecule sensitivity. In this communication, we demonstrate the facile synthesis of 5, 8, and 18 nm gold particle groupings on a well-defined DNA template by hybridizing monoconjugated gold-DNA building blocks. The obtained nanometer interparticle gaps should yield local intensity enhancements up to 4 orders of magnitude as estimated by Generalized Mie Theory. By tuning the particle size and relative curvatures, we calculate that the maximum enhancement can be optimized and localized on a specific part of the nanostructure. These groupings act as plasmon-based nanolenses assembled on a biomolecular backbone that can be functionalized in proximity to the region of highest field.

Optical and Topological Characterization of Gold Nanoparticle Dimers Linked by a Single DNA Double Strand

We demonstrate that symmetric or asymmetric gold nanoparticle dimers with substantial scattering cross sections and plasmon coupling can be produced with a perfectly controlled chemical environment and a high purity using a single DNA linker as short as 7 nm. A statistical analysis of the optical properties and morphology of single dimers is performed using darkfield and cryo-electron microscopies. These results, correlated to Mie theory calculations, indicate that the particle dimers are stretched in water by electrostatic interactions.

Accelerated single photon emission from dye molecule-driven nanoantennas assembled on DNA.

A photon interacts efficiently with an atom when its frequency corresponds exactly to the energy between two eigenstates. But at the nanoscale, homogeneous and inhomogeneous broadenings strongly hinder the ability of solid-state systems to absorb, scatter or emit light. By compensating the impedance mismatch between visible wavelengths and nanometre-sized objects, optical antennas can enhance light-matter interactions over a broad frequency range. Here we use a DNA template to introduce a single dye molecule in gold particle dimers that act as antennas for light with spontaneous emission rates enhanced by up to two orders of magnitude and single photon emission statistics. Quantitative agreement between measured rate enhancements and theoretical calculations indicate a nanometre control over the emitter-particle position while 10 billion copies of the target geometry are synthesized in parallel. Optical antennas can thus tune efficiently the photo-physical properties of nano-objects by precisely engineering their electromagnetic environment.

All-Dielectric Silicon Nanogap Antennas To Enhance the Fluorescence of Single Molecules

Plasmonic antennas have a profound impact on nanophotonics as they provide efficient means to manipulate light and enhance light-matter interactions at the nanoscale. However, the large absorption losses found in metals can severely limit the plasmonic applications in the visible spectral range. Here, we demonstrate the effectiveness of an alternative approach using all-dielectric nanoantennas based on silicon dimers to enhance the fluorescence detection of single molecules. The silicon antenna design is optimized to confine the near-field intensity in the 20 nm nanogap and reach a 270-fold fluorescence enhancement in a nanoscale volume of λ(3)/1800 with dielectric materials only. Our conclusions are assessed by combining polarization resolved optical spectroscopy of individual antennas, scanning electron microscopy, numerical simulations, fluorescence lifetime measurements, fluorescence burst analysis, and fluorescence correlation spectroscopy. This work demonstrates that all-silicon nanoantennas are a valid alternative to plasmonic devices for enhanced single molecule fluorescence sensing, with the additional key advantages of reduced nonradiative quenching, negligible heat generation, cost-efficiency, and complementary metal-oxide-semiconductor (CMOS) compatibility.

Reversible switching of the interparticle distance in DNA-templated gold nanoparticle dimers.

We produce gold nanoparticle dimers with a surface-to-surface distance that varies reversibly by a factor of 3 when hybridizing or removing a single target DNA strand. The dimers are built on one DNA template that features a stem-loop enabling the interparticle distance change. Using electrophoresis, we reach 90% sample purities and demonstrate that this chemical process is reversible in solution at room temperature for a low molar excess of the target DNA strand. The kinetics of the reaction is asymmetric due to steric hindrance in the stem-loop opening process. Furthermore, a statistical analysis of cryo-electron microscopy measurements allows us to provide the first quantitative analysis of distance changes in chemically switchable nanoparticle assemblies.

Wafer Scale Formation of Monocrystalline Silicon-Based Mie Resonators via Silicon-on-Insulator Dewetting

Subwavelength-sized dielectric Mie resonators have recently emerged as a promising photonic platform, as they combine the advantages of dielectric microstructures and metallic nanoparticles supporting surface plasmon polaritons. Here, we report the capabilities of a dewetting-based process, independent of the sample size, to fabricate Si-based resonators over large scales starting from commercial silicon-on-insulator (SOI) substrates. Spontaneous dewetting is shown to allow the production of monocrystalline Mie-resonators that feature two resonant modes in the visible spectrum, as observed in confocal scattering spectroscopy. Homogeneous scattering responses and improved spatial ordering of the Si-based resonators are observed when dewetting is assisted by electron beam lithography. Finally, exploiting different thermal agglomeration regimes, we highlight the versatility of this technique, which, when assisted by focused ion beam nanopatterning, produces monocrystalline nanocrystals with ad hoc size, position, and organization in complex multimers.

Crucial role of the emitter–particle distance on the directivity of optical antennas

We demonstrate that the reflecting properties of a single particle nanoantenna can be extremely sensitive to its distance from a quantum emitter at frequencies lower than the plasmon resonance. The phenomenon is shown to arise from rapid phase variations of the emitter field at short distances associated with a phase of the antenna particle polarizability lower than π/4.

Encoding multipolar polarization patterns by optical poling in polymers: towards nonlinear optical memories

We demonstrate spatially resolved polarization encoding of nonlinear information by all-optical poling of photoisomerizable and nonlinear molecules in polymer films. The second harmonic generation (SHG)polarization responses of the photo-induced patterns are imaged by a nonlinear microscope with 2 microm lateral resolution. The strong SHG dependence to the poling fields polarizations is applied to information encoding, with a potential in high density optical data storage. In addition, the imprinted local nonlinear susceptibilities of multipolar symmetries cannot be deciphered by more traditional one-photon holography techniques.

Photonic engineering of hybrid metal-organic chromophores.

An aureate dye: Confined electromagnetic fields in DNA-templated gold nanoparticle dimers were tuned to engineer the fluorescence properties of organic dyes in water (see picture). Purified suspensions of hybrid metal-organic chromophores featured unprecedented photophysical properties, such as a short lifetime and low quantum yield but high brightness.

Role of spatial distortions on the quadratic nonlinear optical properties of octupolar organic and metallo-organic molecules.

Following on the recent experimental demonstration of a discrepancy between the nonlinear optical (NLO) behavior of several pi-conjugated chromophores and their assumed octupolar symmetry, the authors investigate how geometrical distortions influence the NLO response of multipolar push-pull molecules. Their analytical model is set on a basis of valence-bond and charge-transfer states to estimate the hyperpolarizability of organic and metallo-organic chromophores using the lowest possible number of variables. Since symmetry breakdown changes the definition of the molecular Cartesian framework, tensorial spherical coordinates are implemented. The evolution of the nonlinear molecular anisotropy with possible rotational deviations is then evaluated for two recently studied chromophores. Zero-frequency calculations show that, outside optical resonance, weak geometrical distortions lead to strong anisotropy variations in agreement with experimental data. Their goal is to underscore which molecular engineering strategies should be applied when designing a photoisomerizable nonlinear octupole.