Critical coupling and extreme confinement in nanogap antennas.

Nanogap antennas are compelling structures for squeezing light into ultrasmall volumes. However, when gaps are shrunk to the nanometer scale, the mode losses dramatically increase. In this Letter, we report the conditions of critical coupling between the arrays of nanogap resonant metal-insulator-metal (MIM) antennas and free space. Adapting the antenna density, critical coupling is achievable for any thickness of insulator, from 100 down to 0.1 nm. The fundamental optical mode can be described as continuous transitions through three types of modes: a perfect MIM mode, coupling between the MIM mode and surface plasmon polariton, and a gap plasmon mode. We found that the space between adjacent antennas is an essential parameter to perform critical coupling for thinner gaps. These results pave the way towards understanding extreme confinement in nanogap antenna structures such as MIM or nanoparticle arrays.

Influence of Cracks on the Optical Properties of Silver Nanocrystals Supracrystal Films.

Physical properties of nanocrystals self-assembled into 3D superlattices called supracrystals are highly specific with unexpected behavior. The best example to support such a claim was given through STM/STS experiments at low temperature of very thick supracrystals (around 1000 layers) where it was possible to image the surpracrystal surface and study their electronic properties. From previous studies, we know the optical properties of Ag nanocrystals self-assembled in a hexagonal network two-dimensional (2D) or by forming small 3D superlattices (from around 2 to 7 layers) are governed by dipolar interactions. Here, we challenge to study the optical properties of Ag supracrystals film characterized by large thicknesses (from around 27 to 180 Ag nanocrystals layers). In such experimental conditions, according to the classical Beer-Lambert law, the absorption of Ag films is expected to be very large, and the film transmission is close to zero. Very surprisingly, we observe reduced transmission intensity with an increase of the notch line width, in the 300-800 nm wavelength range, as the supracrystal film thickness increased. By calculating the transmission through the supracrystal films, we deduced that the films were dominated by the presence of cracks with wetting layers existing at their bottoms. This result was also confirmed by optical micrographs. The cracks widths increased with increasing the film thickness leading to more complex wetting layers. We also demonstrated the formation of small Ag clusters at the nanocrystal surface. These results provide some implications toward the design of plasmonic materials.

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays.

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavities when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties.

Plasmon lasers: coherent nanoscopic light sources.

Plasmon lasers are a new class of coherent light sources that use metals for light localization and amplification. Access to this confined light that couples to the oscillating electrons of metal enables reducing the physical size and mode volume of the laser much below the diffraction limit. The race to demonstrate new plasmon nanolasers has enabled considerable progress over the last several years regarding nanocavity design, operating temperature, pumping conditions, and material efficiency of both plasmonic nanocavity and gain medium. This article discusses some of the latest developments of coherent nanoscopic light sources, in metallic and dielectric lasers, with a specific focus on plasmon nanolasers. We highlight recent advances in plasmon lasers through plasmonic nanoparticle arrays: beam directionality, wavelength tunability, multi-modal emission, and dark and bright modes lasing. We also discuss future prospects.

Water-Dispersed Hydrophobic Au Nanocrystal Assemblies with a Plasmon Fingerprint.

Hydrophobic Au nanocrystal assemblies (both ordered and amorphous) were dispersed in aqueous solution via the assistance of lipid vesicles. The intertwine between vesicles and Au assemblies was made possible through a careful selection of the length of alkyl chains on Au nanocrystals. Extinction spectra of Au assemblies showed two peaks that were assigned to a scattering mode that red-shifted with increasing the assembly size and an absorption mode associated with localized surface plasmon that was independent of their size. This plasmon fingerprint could be used as a probe for investigating the optical properties of such assemblies. Our water-soluble assemblies enable exploring a variety of potential applications including solar energy and biomedicine.

Real-time tunable lasing from plasmonic nanocavity arrays.

Plasmon lasers can support ultrasmall mode confinement and ultrafast dynamics with device feature sizes below the diffraction limit. However, most plasmon-based nanolasers rely on solid gain materials (inorganic semiconducting nanowire or organic dye in a solid matrix) that preclude the possibility of dynamic tuning. Here we report an approach to achieve real-time, tunable lattice plasmon lasing based on arrays of gold nanoparticles and liquid gain materials. Optically pumped arrays of gold nanoparticles surrounded by liquid dye molecules exhibit lasing emission that can be tuned as a function of the dielectric environment. Wavelength-dependent time-resolved experiments show distinct lifetime characteristics below and above the lasing threshold. By integrating gold nanoparticle arrays within microfluidic channels and flowing in liquid gain materials with different refractive indices, we achieve dynamic tuning of the plasmon lasing wavelength. Tunable lattice plasmon lasers offer prospects to enhance and detect weak physical and chemical processes on the nanoscale in real time.

Plasmon-based free-radical photopolymerization: effect of diffusion on nanolithography processes.

This Article interrogates the mechanisms responsible for nanoscale photopolymerization induced by confined and enhanced electromagnetic fields. Surface plasmon dipolar resonance of individual Ag nanoparticles was used as an optical near-field source to locally trigger the reaction of a photopolymerizable formulation. Laser excitation of the nanoparticles embedded in the formulation reproducibly generates polymer features with typical dimensions ranging from 2 nm to a few tens of nanometer. We have determined the physicochemical parameters and mechanisms controlling the spatial extent of the photopolymerization process. We found that the diffusion of the dye is the main process limiting the polymerization reaction, as opposed to what is observed at the microscale with an equivalent chemical system. This approach demonstrates that plasmon-based polymerization can achieve true nanometer scale resolution and also provides a unique opportunity to investigate photochemistry at this length scale.

Off-Resonant Optical Excitation of Gold Nanorods: Nanoscale Imprint of Polarization Surface Charge Distribution.

We report on the nanoscale optical characterization of gold nanorods irradiated out of their plasmonic resonance. Our approach is based on the reticulation of a photopolymerizable formulation locally triggered by enhanced electromagnetic fields. The tiny local field enhancement stems from the surface polarization charges associated with the electric field discontinuity at the metal/dielectric interface. This allows us to get a nanoscale signature of the spatial distribution of the surface charge density in metallic nanoparticles irradiated off-resonance.

Quantitative analysis of localized surface plasmons based on molecular probing.

We report on the quantitative characterization of the plasmonic optical near-field of a single silver nanoparticle. Our approach relies on nanoscale molecular molding of the confined electromagnetic field by photoactivated molecules. We were able to directly image the dipolar profile of the near-field distribution with a resolution better than 10 nm and to quantify the near-field depth and its enhancement factor. A single nanoparticle spectral signature was also assessed. This quantitative characterization constitutes a prerequisite for developing nanophotonic applications.