Mathieu Mivelle

A plasmonic /`antenna-in-box/' platform for enhanced single-molecule analysis at micromolar concentrations

Single-molecule fluorescence techniques are key for a number of applications, including DNA sequencing, molecular and cell biology and early diagnosis. Unfortunately, observation of single molecules by diffraction-limited optics is restricted to detection volumes in the femtolitre range and requires pico- or nanomolar concentrations, far below the micromolar range where most biological reactions occur. This limitation can be overcome using plasmonic nanostructures, which enable the confinement of light down to nanoscale volumes. Although these nanoantennas enhance fluorescence brightness, large background signals and/or unspecific binding to the metallic surface have hampered the detection of individual fluorescent molecules in solution at high concentrations. Here we introduce a novel antenna-in-box platform that is based on a gap-antenna inside a nanoaperture. This design combines fluorescent signal enhancement and background screening, offering high single-molecule sensitivity (fluorescence enhancement up to 1,100-fold and microsecond transit times) at micromolar sample concentrations and zeptolitre-range detection volumes. The antenna-in-box device can be optimized for single-molecule fluorescence studies at physiologically relevant concentrations, as we demonstrate using various biomolecules.

Diabolo nanoantenna for enhancing and confining the magnetic optical field.

In this Letter, we introduce a new nanoantenna concept aimed at generating a single magnetic hot spot in the optical frequency range, thus confining and enhancing the magnetic optical field on the background of a much lower electric field. This nanoantenna, designed by applying Babinets principle to the bowtie nanoaperture, takes the shape of a diabolo. It differs from the well-known bowtie nanoantenna in that the opposing pair of metal triangles are electrically connected through their facing tips. Thus instead of a large charge density accumulating at the air gap of the bowtie nanoantenna, leading to a large electric field, a high optical current density develops within the central metal gap of the diabolo nanoantenna, leading to a large magnetic field. Numerical simulation results on the first nanodiabolo geometries show a 2900-fold enhancement of the magnetic field at a wavelength of 2540 nm, confined to a 40-by-40 nm region near the center of the nanoantenna.

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.

Ultrabright Bowtie Nanoaperture Antenna Probes Studied by Single Molecule Fluorescence

We report on a novel design for the fabrication of ultrabright bowtie nanoaperture antenna (BNA) probes to breach the intrinsic trade-off between power transmission and field confinement of circular nanoapertures as in near-field scanning optical microscopy (NSOM) or planar zero mode waveguides. The approach relies on the nanofabrication of BNAs at the apex of tapered optical fibers tuned to diameters close to their cutoff region, resulting in 10(3)× total improvement in throughput over conventional NSOM probes of similar confinement area. By using individual fluorescence molecules as optical nanosensors, we show for the first time nanoimaging of single molecules using BNA probes with an optical confinement of 80 nm, measured the 3D near-field emanating from these nanostructures and determined a ~6-fold enhancement on the single molecule signal. The broadband field enhancement, nanoscale confinement, and background free illumination provided by these nanostructures offer excellent perspectives as ultrabright optical nanosources for a full range of applications, including cellular nanoimaging, spectroscopy, and biosensing.

Matching Nanoantenna Field Confinement to FRET Distances Enhances Förster Energy Transfer Rates

Förster resonance energy transfer (FRET) is widely applied in chemistry, biology, and nanosciences to assess distances on sub-10 nm scale. Extending the range and applicability of FRET requires enhancement of the fluorescence energy transfer at a spatial scale comparable to the donor-acceptor distances. Plasmonic nanoantennas are ideal to concentrate optical fields at a nanoscale fully matching the FRET distance range. Here, we present a resonant aluminum nanogap antenna tailored to enhance single molecule FRET. A 20 nm gap confines light into a nanoscale volume, providing a field gradient on the scale of the donor-acceptor distance, a large 10-fold increase in the local density of optical states, and strong intensity enhancement. With our dedicated design, we obtain 20-fold enhancement on the fluorescence emission of donor and acceptor dyes, and most importantly up to 5-fold enhancement of the FRET rate for donor-acceptor separations of 10 nm. We also provide a thorough framework of the fluorescence photophysics occurring in the nanoscale gap volume. The presented enhancement of energy transfer flow at the nanoscale opens a yet unexplored facet of the various advantages of optical nanoantennas and provides a new strategy toward biological applications of single molecule FRET at micromolar concentrations.

Large-Scale Arrays of Bowtie Nanoaperture Antennas for Nanoscale Dynamics in Living Cell Membranes

We present a novel blurring-free stencil lithography patterning technique for high-throughput fabrication of large-scale arrays of nanoaperture optical antennas. The approach relies on dry etching through nanostencils to achieve reproducible and uniform control of nanoantenna geometries at the nanoscale, over millimeter-sizes in a thin aluminum film. We demonstrate the fabrication of over 400 000 bowtie nanoaperture (BNA) antennas on biocompatible substrates, having gap sizes ranging from (80 ± 5) nm down to (20 ± 10) nm. To validate their applicability on live cell research, we used the antenna substrates as hotspots of localized illumination to excite fluorescently labeled lipids on living cell membranes. The high signal-to-background afforded by the BNA arrays allowed the recording of single fluorescent bursts corresponding to the passage of freely diffusing individual lipids through hotspot excitation regions as small as 20 nm. Statistical analysis of burst length and intensity together with simulations demonstrate that the measured signals arise from the ultraconfined excitation region of the antennas. Because these inexpensive antenna arrays are fully biocompatible and amenable to their integration in most fluorescence microscopes, we foresee a large number of applications including the investigation of the plasma membrane of living cells with nanoscale resolution at endogenous expression levels.

Hybrid photonic antennas for subnanometer multicolor localization and nanoimaging of single molecules.

Photonic antennas amplify and confine optical fields at the nanoscale offering excellent perspectives for nanoimaging and nanospectroscopy. Increased resolution beyond the diffraction limit has been demonstrated using a variety of antenna designs, but multicolor nanoscale imaging is precluded by their resonance behavior. Here we report on the design of a novel hybrid antenna probe based on a monopole nanoantenna engineered on a bowtie nanoaperture. The device combines broadband enhanced emission, extreme field confinement down to few nanometers, and zero-background illumination. We demonstrate simultaneous dual-color single molecule nanoimaging with 20 nm resolution and angstrom localization precision, corresponding to 10(3)-fold improvement compared to diffraction-limited optics. When interacting with individual molecules in the near-field, our innovative design enables the emission of 10(4) photon-counts per molecule in a 20 nm excitation region, allowing direct discrimination of spectrally distinct molecules separated by 2.1 ± 0.4 nm. We foresee that background-free nanolight sources will open new horizons in optical nanoscopy and fluorescence spectroscopy by providing multicolor detection of standard fluorescent molecules fully compatible with live cell research.

Enhancement and Inhibition of Spontaneous Photon Emission by Resonant Silicon Nanoantennas

Substituting noble metals for high-index dielectrics has recently been proposed as an alternative strategy in nanophotonics to design broadband optical resonators and circumvent the ohmic losses of plasmonic materials. In this report, we demonstrate that subwavelength silicon nanoantennas can manipulate the photon emission dynamics of fluorescent molecules. In practice, it is showed that dielectric nanoantennas can both increase and decrease the local density of optical states (LDOS) at room temperature, a process that is inaccessible with noble metals at the nanoscale. Using scanning probe microscopy, we analyze quantitatively, in three dimensions, the near-field interaction between a 100 nm fluorescent nanosphere and silicon nanoantennas with diameters ranging between 170 nm and 250 nm. Associated to numerical simulations, these measurements indicate increased or decreased total spontaneous decay rates by up to 15 % and a gain in the collection efficiency of emitted photons by up to 85 %. Our study demonstrates the potential of silicon-based nanoantennas for the low-loss manipulation of solid-state emitters at the nanoscale and at room temperature.

Nanophotonic Approaches for Nanoscale Imaging and Single-Molecule Detection at Ultrahigh Concentrations

Over the last decade, we have witnessed an outburst of many different optical techniques aimed at breaking the diffraction limit of light, providing super‐resolution imaging on intact fixed cells. In parallel, single‐molecule detection by means of fluorescence has become a common tool to investigate biological interactions at the molecular level both in vitro and in living cells. Despite these advances, visualization of dynamic events at relevant physiological concentrations at the nanometer scale remains challenging. In this review, we focus on recent advancements in the field of nanophotonics toward nanoimaging and single‐molecule detection at ultrahigh sample concentrations. These approaches rely on the use of metal nanostructures known as optical antennas to localize and manipulate optical fields at the nanometer scale. We highlight examples on how different optical antenna geometries are being implemented for nanoscale imaging of cell membrane components. We also discuss different implementations of self‐standing and two‐dimensional antenna arrays for studying nanoscale dynamics in living cell membranes as well as detection of individual biomolecular interactions in the µM range for sensing applications. Microsc. Res. Tech. 77:537–545, 2014.

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.