Light, nanomaterials, nanotechnologies

International audience

Abstract Rapid plasmonic biosensing has attracted wide attention in early disease diagnosis and molecular biology research. However, it was still challenging for conventional angle-interrogating plasmonic sensors to obtain higher sensitivity without secondary amplifying labels such as plasmonic nanoparticles. To address this issue, we developed a plasmonic biosensor based on the enhanced lateral position shift by phase singularity. Such singularity presents as a sudden phase retardation at the dark point of reflection from resonating plasmonic substrate, leading to a giant position shift on reflected beam. Herein, for the first time, the atomically thin layer of Ge 2 Sb 2 Te 5 (GST) on silver nanofilm was demonstrated as a novel phase-response-enhancing plasmonic material. The GST layer was not only precisely engineered to singularize phase change but also served as a protective layer for active silver nanofilm. This new configuration has achieved a record-breaking largest position shift of 439.3 μm measured in calibration experiments with an ultra-high sensitivity of 1.72 × 10 8 nm RIU −1 (refractive index unit). The detection limit was determined to be 6.97 × 10 −7 RIU with a 0.12 μm position resolution. Besides, a large figure of merit (FOM) of 4.54 × 10 11 μm (RIU∙°) −1 was evaluated for such position shift interrogation, enabling the labelfree detection of trace amounts of biomolecules. In targeted biosensing experiments, the optimized sensor has successfully detected small cytokine biomarkers (TNF-α and IL-6) with the lowest concentration of 1 × 10 −16 M. These two molecules are the key proinflammatory cancer markers in clinical diagnosis, which cannot be directly screened by current clinical techniques. To further validate the selectivity of our sensing systems, we also measured the affinity of integrin binding to arginylglycylaspartic acid (RGD) peptide (a key protein interaction in cell adhesion) with different Mn 2+ ion concentrations, ranging from 1 nM to 1 mM.

Zinc oxide (ZnO) is a stable, direct bandgap semiconductor emitting in the UV with a multitude of technical applications. It is well known that ZnO emission can be shifted into the green for visible light applications through the introduction of defects. However, generating consistent and efficient green emission through this process is challenging, particularly given that the chemical or atomic origin of the green emission in ZnO is still under debate. In this work we present a new method, for which we coin term desulfurization, for creating green emitting ZnO with significantly enhanced quantum efficiency. Solution grown ZnO nanowires are partially converted to ZnS, then desulfurized back to ZnO, resulting in a highly controlled concentration of oxygen defects as determined by X-ray photoelectron spectroscopy and electron paramagnetic resonance. Using this controlled placement of oxygen vacancies we observe a greater than 40-fold enhancement of integrated emission intensity and explore the nature of this enhancement through low temperature photoluminescence experiments.

Optical modulators are essential components in optical communication and photonic neuromorphic networks. Graphene on silicon waveguides have been proposed for optical modulation but the modulation depth is limited to 0.1 dB/μm. Higher modulation depth and shorter modulators can be achieved with plasmonic modes; however, due to its transverse magnetic nature, they weakly interact with graphene. In this contribution, a plasmonic Bloch mode supported by a plasmonic waveguide is used to overcome this problem. Its high in-plane electric field strongly interacts with graphene. Numerical results show modulation depths of 4 dB/μm at 1.65 μm with 2.6 dB loss. A subwavelength footprint of 0.5 μm2 allows a modulation speed of up to 39 GHz and an energy consumption of 21.2 fJ/b. This sub-λ size modulator is a promising candidate for optical communication and neuromorphic circuits.

We systematically investigate the metallic photoluminescence (MPL) emitted from plasmonic nanoparticles (NPs) upon excitation with ultrafast laser pulses using a scanning confocal optical microscope (SCOM). By comparing the emission spectra of Au NPs of varying dimensions with the corresponding dark-field scattering spectra, indications are found that MPL encompasses two emission channels: the particle plasmons (PPs) and the electron-hole (e-h) pair recombination. The plasmons can be interpreted to play a twofold role: in the excitation process they provide the local field enhancement, and in the emission process they offer extra radiation channels.

In the context of using portions of a photosynthetic apparatus of green plants and photosynthesizing bacteria in bioinspired photovoltaic systems, we consider possible control of the chlorophyll excited state decay rate using nanoantennas in the form of a single metal and semiconductor nanoparticle. Since chlorophyll luminescence competes with electron delivery for chemical reactions chain and also to an external circuit, we examine possible excited state decay inhibition contrary to radiative rate enhancement. Both metal and semiconductor nanoparticles enable inhibition of radiative decay rate by one order of the magnitude as compared to that in vacuum, whereas a metal nanosphere cannot perform the overall decay inhibition since slowing down of radiative decay occurs only along with the similar growth of its nonradiative counterpart whereas a semiconductor nanoantenna is lossless. Additionally, at normal orientation of the emitter dipole moment to a nanoparticle surface, a silicon nanoparticle promotes enhancement of radiative decay by one order of the magnitude within the whole visible range. Our results can be used for other photochemical or photovoltaic processes, and strong radiative decay enhancement found for dielectric nanoantennas paves the way to radiative decays and light emitters engineering without non-radiative losses.

A major challenge towards nanophotonics is the integration of nanoemitters on optical chips. Combining the optical properties of nanoemitters with the benefits of integration and scalability of integrated optics is still a major issue to overcome. In this work, we demonstrate the integration of nanoemitters positioned in a controlled manner onto a substrate and onto an optical ion-exchanged glass waveguide via direct laser writing based on two-photon polymerization. Our nanoemitters are colloidal CdSe/ZnS quantum dots (QDs) embedded in polymeric nanostructures. By varying the laser parameters during the patterning process, we make size-controlled QD-polymer nanostructures that were systematically characterized using optical and structural methods. Structures as small as 17 nm in height were fabricated. The well-controlled QD-polymer nanostructure systems were then successfully integrated onto a new photonic platform for nanophotonics made of an ion-exchanged waveguide. We show that our QDs maintain their light emitting quality after integration as verified by photoluminescence (PL) measurements. Ultimately, QD emission coupled to our waveguides is detected through a home-built fiber-edge coupling PL measurement setup. Our results show the potential for future integration of nanoemitters onto complex photonic chips.

The optical characterization of a single metallic nanostructure has a strong interest in the scientific community owing to its localized surface plasmon resonances. For a single nano-object, the simplest and the accepted optical characterization technique is dark-field spectroscopy, even if there are many drawbacks and a certain complexity to operate it. We propose here using extinction spectroscopy of nanoparticles ensembles to characterize optically a single nanostructure. The scattering spectrum of a single gold nanocylinder and the extinction spectrum of a well-chosen array show similar results. We perform an experimental and numerical comparative study to draw parallels between both techniques.

Surface plasmon polaritons (SPPs) are surface modes confined to metal-dielectric interfaces. This confinement enhances the electromagnetic field and therefore, SPPs are sensitive to surface conditions. The properties of two dimensional materials such as graphene thus can be enhanced and used to engineer nanoscale components for optical communications. However, SPPs are transverse magnetic modes with electric fields out-of-plane that limit flexibility. In this contribution, we numerically analyze the confinement and in-plane enhancement in graphene-based hybrid plasmonic waveguides. We find that plasmonic modes supported by metal nanoparticle chain waveguides provide higher in-plane enhancement compared to those supported by nano-strip and slot hybrid plasmonic waveguides. Our results contribute to the performance improvement of graphene light absorption devices, including electro-optic modulators and photodetectors.

We evaluate experimentally and theoretically the role of the residual ligands and ambient environment refractive index in the optical response of a single spherical gold nanoparticle on a substrate and demonstrate the changes in the near- and far-field properties of its hybridized modes in the presence of the cetyltrimethylammonium bromide (CTAB) layer. Particularly, we show that the conventional bilayer scheme for CTAB is not relevant for colloidal nanoparticles deposited on a substrate. We show that this CTAB layer considerably changes the amplitude and localization of the confinement of the electric field, which is of prime importance in the design of plasmonic complex systems coupled to emitters. Moreover, we numerically study the influence of the CTAB layer on the modification of sensitivity of plasmonic resonances of a gold nanopshere to local refractive index changes.

International audience

Integrated metaphotonic devices has opened new horizons to control light-guiding properties at nanoscale; particularly interesting is the application of plasmonic nanostructures coupled to dielectric waveguides to reduce the inherent light propagation losses in metallic metamaterials. In this contribution, we show the feasibility of using ion-exchanged glass waveguides (IExWg) as a platform for the efficient excitation of surface plasmon polaritons (SPP). These IExWg provide high coupling efficiency and low butt-coupling with conventional dielectric optical waveguides and fibers, overcoming the hard fabrication tunability of commonly used CMOS-guiding platforms. We present a near-field scanning optical microscopy characterization of the propagation characteristics of SPP supported in a gold nanoslab fabricated on top of an IExWg. We found that the SPP can be only be excited with the fundamental TM photonic mode of the waveguide. Thanks to the low propagation loss, low birefringence, and compatibility with optical fibers, glass waveguide technology is a promising platform for the development of integrated plasmonic devices operating at visible and near infrared wavelengths with potential applications in single molecule emission routing or biosensing devices.

In this Letter, we engineer the colors of all-dielectric metasurfaces by means of a metamodel-based optimization approach. This algorithm combines heuristic optimization and neural networks to retrieve the metasurface’s optimal geometrical parameters that serve to reproduce a prescribed color. The metasurfaces were fabricated and experimentally validated through dark field optical microscope images. We present typical results for periodic arrays of nanoparticles with arbitrary cross section. The approach is well-suited for color reproduction and is computationally inexpensive.

We propose a metamodel-based optimization technique to tailor the chromatic response of high-contrast-index gratings. The algorithm, which couples a population-based metaheuristic with a neural network, is used to retrieve the optimal geometrical parameters of a grating to reproduce a prescribed color. By means of some examples, we assess the possibilities and limitations of our optimization scheme. The numerical evidence found shows that the metamodel approach offers an alternative to traditional metaheuristic techniques that not only provides the best solution for a given geometry and a material but also significantly improves the computing time required for the optimization process.

In this work, we propose an inversion scheme to tailor the chromatic response of an all-dielectric structure. To this end, we couple, through a previously defined objective functional involving the concept of color difference, a forward solver with an optimization algorithm. The former is based on the differential method, whereas the latter is based on particle swarm optimization. The optimal geometrical parameters of the structure that generates a specific color are obtained through the solution of an approximation problem. We illustrate the performance of our inversion scheme through examples and discuss its limitations and potential applications.

Abstract Coupled localized surface plasmon resonances (LSPRs) in periodic arrays of metallic nanowires are attractive for use in sensing applications due to their light enhancement and their sensitivity to the surrounding environment. Due to the interwire coupling, they behave as plasmonic waveguides with high wavevector modes that require bulky methods for efficient excitation. In this contribution, we demonstrate the excitation of coupled LSPRs in gold nanowires with photonic modes supported by an optical waveguide made with ion exchange technology. Currently, although weakly-coupled LSPRs are experimentally demonstrated, strongly-coupled LSPRs are only demonstrated numerically due to the challenge represented by the fabrication of a high density nanowire array with current electron beam lithography. Due to their operation across the visible spectrum and its low-loss coupling to standard optical fibers, integrated nanowires on glass waveguides open new perspectives for the development of hybrid photonic-plasmonic integrated optical devices.

International audience

In this work, we discuss excitation of orthogonal and parallel collective resonances in rectangular arrays of aluminum nanoparticles and switch between them with a change of array dimensions or polarization. We demonstrate that in the case of the substrate, scattered fields from nanoparticles can interact with each other in directions both parallel and orthogonal to the external electric field, which results in manifestation of the parallel coupling when localized plasmon resonance is near its spectral position. In this work, the parallel diffraction waves couple with in-plane quadrupolar mode excited with a scattered field coming from the neighboring nanoparticles. The rate of the parallel coupling depends on the interparticle distance, which allows us to control the intensity of the coupled mode.

Here, reciprocity and Babinet's principles were applied to the design of integrated plasmonic structures on silicon photonic waveguides. Numerical analyses and near-field optical microscopy observations show that one of the hybrid photonic-plasmonic structures exhibits high confinement and enhancement of the electric field, and, through Babinet's principle, the magnetic field of its complementary structure is confined and enhanced as well. Reciprocally, due to the modification of the electric and magnetic local density of states, enhanced emission of electric and magnetic dipoles by Purcell effect were obtained into specific silicon photonic modes. Such structures can be advantageously implemented for on-chip integrated single-photon sources.

The optical properties of a monolayer of nanocomposite film (PMMA/gold nanocubes) were provided by fitting a proposed theoretical model to spectroscopic ellipsometry (SE) measurements. For such a thin film, these features cannot be successfully determined by means of experimental and conventional effective medium theory such as Maxwell-Garnett or Bruggeman. To make it possible, we developed a model of two classical Lorentz oscillators; one for a PMMA layer and the other for GNCs, revealing one homogeneous layer and rapid analysis without the need for large computational resources. Additionally, we tailored both the size and number of GNCs in the PMMA layer by tuning the synthesis parameters as seen in scanning electron microscopy (SEM) images. In parallel, SE measurements clearly highlighted the change in the optical properties of GNCs as a function of their density on the substrate and dimensions. Our findings demonstrate that SE is an alternative method to characterize layered GNCs on opaque substrates efficiently, which has potential implications for designing other morphologies in the future.