Jérémy Butet

Optical Second Harmonic Generation of Single Metallic Nanoparticles Embedded in a Homogeneous Medium

We report the optical second harmonic generation from individual 150 nm diameter gold nanoparticles dispersed in gelatin. The quadratic hyperpolarizability of the particles is determined and the input polarization dependence of the second harmonic intensity obtained. These results are found in excellent agreement with ensemble measurements and finite element simulations. These results open up new perspectives for the investigation of the nonlinear optical properties of noble metal nanoparticles.

Optical Second Harmonic Generation in Plasmonic Nanostructures: From Fundamental Principles to Advanced Applications

Plasmonics has emerged as an important research field in nanoscience and nanotechnology. Recently, significant attention has been devoted to the observation and the understanding of nonlinear optical processes in plasmonic nanostructures, giving rise to the new research field called nonlinear plasmonics. This review provides a comprehensive insight into the physical mechanisms of one of these nonlinear optical processes, namely, second harmonic generation (SHG), with an emphasis on the main differences with the linear response of plasmonic nanostructures. The main applications, ranging from the nonlinear optical characterization of nanostructure shapes to the optimization of laser beams at the nanoscale, are summarized and discussed. Future directions and developments, made possible by the unique combination of SHG surface sensitivity and field enhancements associated with surface plasmon resonances, are also addressed.

Augmenting Second Harmonic Generation Using Fano Resonances in Plasmonic Systems

Significant augmentation of second harmonic generation using Fano resonances in plasmonic heptamers made of silver is theoretically and experimentally demonstrated. The geometry is engineered to simultaneously produce a Fano resonance at the fundamental wavelength, resulting in a strong localization of the fundamental field close to the system, and a higher order scattering peak at the second harmonic wavelength. These results illustrate the versatility of Fano resonant structures to engineer specific optical responses both in the linear and nonlinear regimes thus paving the way for future investigations on the role of dark modes in nonlinear and quantum optics.

Origin of optical second-harmonic generation in spherical gold nanoparticles: Local surface and nonlocal bulk contributions

The second-harmonic generation of 150 nm spherical gold nanoparticles is investigated both experimentally and theoretically. We demonstrate that the interference effects between dipolar and octupolar plasmons can be used as a fingerprint to discriminate the local surface and non-local bulk contributions to the second-harmonic generation. By fitting the experimental data with the electric fields computed with finite-element method (FEM) simulations, the Rudnick and Stern parameters weighting the relative nonlinear sources efficiencies are evaluated and the validity of the hydrodynamic model and the local density approximation approaches are discussed.

Sensing with Multipolar Second Harmonic Generation from Spherical Metallic Nanoparticles

We show that sensing in the nonlinear optical regime using multipolar surface plasmon resonances is more sensitive in comparison to sensing in the linear optical regime. Mie theory, and its extension to the second harmonic generation from a metallic nanosphere, is used to describe multipolar second harmonic generation from silver metallic nanoparticles. The standard figure of merit of a potential plasmonic sensor based on this principle is then calculated. We finally demonstrate that such a sensor is more sensitive to optical refraction index changes occurring in the vicinity of the metallic nanoparticle than its linear counterpart.

Ultrasensitive Optical Shape Characterization of Gold Nanoantennas Using Second Harmonic Generation

Second harmonic generation from plasmonic nanoantennas is investigated numerically using a surface integral formulation for the calculation of both the fundamental and the second harmonic electric field. The comparison between a realistic and an idealized gold nanoantenna shows that second harmonic generation is extremely sensitive to asymmetry in the nanostructure shape even in cases where the linear response is barely modified. Interestingly, minute geometry asymmetry and surface roughness are clearly revealed by far-field analysis, demonstrating that second harmonic generation is a promising tool for the sensitive optical characterization of plasmonic nanostructures. Furthermore, defects located where the linear field is strong (e.g., in the antenna gap) do not necessarily have the strongest impact on the second harmonic signal.

Nanoscale topographical control of capillary assembly of nanoparticles

Predetermined and selective placement of nanoparticles onto large-area substrates with nanometre-scale precision is essential to harness the unique properties of nanoparticle assemblies, in particular for functional optical and electro-optical nanodevices. Unfortunately, such high spatial organization is currently beyond the reach of top-down nanofabrication techniques alone. Here, we demonstrate that topographic features comprising lithographed funnelled traps and auxiliary sidewalls on a solid substrate can deterministically direct the capillary assembly of Au nanorods to attain simultaneous control of position, orientation and interparticle distance at the nanometre level. We report up to 100% assembly yield over centimetre-scale substrates. We achieve this by optimizing the three sequential stages of capillary nanoparticle assembly: insertion of nanorods into the traps, resilience against the receding suspension front and drying of the residual solvent. Finally, using electron energy-loss spectroscopy we characterize the spectral response and near-field properties of spatially programmable Au nanorod dimers, highlighting the opportunities for precise tunability of the plasmonic modes in larger assemblies.

Nonlinear Plasmonic Nanorulers

The evaluation of distances as small as few nanometers using optical waves is a very challenging task that can pave the way for the development of new applications in biotechnology and nanotechnology. In this article, we propose a new measurement method based on the control of the nonlinear optical response of plasmonic nanostructures by means of Fano resonances. It is shown that Fano resonances resulting from the coupling between a bright mode and a dark mode at the fundamental wavelength enable unprecedented and direct manipulation of the nonlinear electromagnetic sources at the nanoscale. In the case of second harmonic generation from gold nanodolmens, the different nonlinear sources distributions induced by the different coupling regimes are clearly revealed in the far-field distribution. Hence, the configuration of the nanostructure can be accurately determined in 3-dimensions by recording the wave scattered at the second harmonic wavelength. Indeed, the conformation of the different elements building the system is encoded in the nonlinear far-field distribution, making second harmonic generation a promising tool for reading 3-dimension plasmonic nanorulers. Furthemore, it is shown that 3-dimension plasmonic nanorulers can be implemented with simpler geometries than in the linear regime while providing complete information on the structure conformation, including the top nanobar position and orientation.

Second-harmonic generation from periodic arrays of arbitrary shape plasmonic nanostructures: a surface integral approach

A surface integral formulation for the second-harmonic generation (SHG) from periodic metallic–dielectric nanostructures is described. This method requires the discretization of the scatterers’ surface in the unit cell only. All the physical quantities involved in this problem are derived in the unit cell by applying specific periodic boundary conditions both at the fundamental and the second-harmonic (SH) frequencies. Both the fundamental and the SH electric fields are computed using the method of moments and periodic Green’s function evaluated with the Ewald’s method. The accuracy of the method is carefully assessed using two specific cases, namely the surface plasmon enhancement of SHG from a gold film and the SHG from L-shaped nanoparticle arrays. These two examples emphasize the accuracy and versatility of the proposed method, which can be applied to a broad range of periodic metallic structures, including plasmonic arrays on arbitrary substrates and metamaterials.

Mode analysis of second-harmonic generation in plasmonic nanostructures

Using a surface integral equation approach based on the tangential Poggio–Miller–Chang–Harrington–Wu–Tsai formulation, we present a full wave analysis of the resonant modes of 3D plasmonic nanostructures. This method, combined with the evaluation of second-harmonic generation, is then used to obtain a better understanding of their nonlinear response. The second-harmonic generation associated with the fundamental dipolar modes of three distinct nanostructures (gold nanosphere, nanorod, and coupled nanoparticles) is computed in the same formalism and compared with the other computed modes, revealing the physical nature of the second-harmonic modes. The proposed approach provides a direct relationship between the fundamental and second-harmonic modes in complex plasmonic systems and paves the way for an optimal design of double resonant nanostructures with efficient nonlinear conversion. In particular, we show that the efficiency of second-harmonic generation can be dramatically increased when the modes with the appropriate symmetry are matched with the second-harmonic frequency.