Plasmonic-Based Mechanochromic Microcapsules as Strain Sensors.

Efficiently detecting mechanical deformations within materials is critical in a wide range of devices, from micro-electromechanical systems to larger structures in the aerospace industry. This communication reports the fabrication of new mechanochromic micrometer-size capsules enabling the detection of strains. These microcapsules are synthesized using an emulsification approach. They are made of densely packed gold nanoparticles embedded in a spherical silica crust. Billions of these composite spherical microcapsules are fabricated in a single batch. Each microcapsule is an opto-mechanosensor by itself, and can easily be recovered and incorporated into polymer films. When the films are stretched, the microcapsules are deformed into elongated ellipsoidal shapes and the distance between the Au NPs embedded in their shells concomitantly increases. As the extinction of Au NPs depends on the separation between the Au NPs, microcapsules exhibit different colors when they are elongated. These novel sensitive microcapsules can be used to detect and measure strain in polymer films by outputting color information.

Plasmon Resonances in Self-Assembled Two-Dimensional Au Nanocrystal Metamolecules.

We explore the evolution of plasmonic modes in two-dimensional nanocrystal oligomer "metamolecules" as the number of nanocrystals is systematically varied. Precise, hexagonally ordered Au nanocrystal oligomers with 1-31 members are assembled via capillary forces into polygonal topographic templates defined using electron-beam lithography. The visible and near-infrared scattering response of individual oligomers is measured by spatially resolved, polarized darkfield scattering spectroscopy. The response is highly sensitive to in-plane versus out-of-plane incident polarization, and we observe an exponentially saturating red shift in plasmon resonance wavelength as the number of nanocrystals per oligomer increases, in agreement with theoretical predictions. Simulations further elucidate the modes supported by the oligomers, including electric dipole and magnetic dipole resonances and their Fano interference. The single-oligomer sensitivity of our measurements also reveals the role of positional disorder in determining the wavelength and character of the plasmonic response. The progression of oligomer metamolecule structures studied here advances our understanding of fundamental plasmonic interactions in the transition regime between few-member plasmonic clusters and extended two-dimensional arrays.

Dendronization-induced phase-transfer, stabilization and self-assembly of large colloidal Au nanoparticles.

The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates.

Topological darkness in self-assembled plasmonic metamaterials.

Self-assembled plasmonic metamaterials are fabricated from silver nanoparticles covered with a silica shell. These metamaterials demonstrate topological darkness or selective suppression of reflection connected to global properties of the Fresnel coefficients. The optical properties of the studied structures are in good agreement with effective medium theory. The results suggest a practical way of achieving high phase sensitivity in plasmonic metamaterials.

Bottom-up fabrication and optical characterization of dense films of meta-atoms made of core-shell plasmonic nanoparticles.

In an attempt to fabricate low index metamaterials by a bottom-up approach, meta-atoms constituted of silica-coated silver nanoparticles are assembled by a Langmuir-Schaefer technique into thin films of large area and well-controlled thickness. The silica shells ensure a constant distance between the silver cores, hence providing a constant coupling of the localized surface plasmon resonance (LSPR) of the nanoparticles in the assembled composite material. The optical response is studied by normal angle spectral reflectance measurements and by variable angle spectroscopic ellipsometry. The normal incidence data are described well in the framework of a single effective Lorentz oscillator model. The resonance of the assembled material is blue-shifted and shows no significant broadening with respect to the absorption band of the individual nanoparticles. The observation of these two effects is enabled by the core-shell structure of the meta-atoms that prevents aggregation of the metallic cores. The ellipsometry study confirms the general behavior and reveals the natural birefringence of the few-layer materials. The amplitude of the observed resonance is weaker than expected from the Maxwell-Garnett mixing rule. This well-characterized system may constitute a good model for numerical simulations.