Optical and thermal activity of plasmon-active nanoparticles in transparent dielectric media is of growing interest in thermal therapies, photovoltaics and optoelectronic components in which localized surface plasmon resonance (LSPR) could play a significant role. This work compares a new method to embed gold nanoparticles (AuNPs) in dense, composite films with an extension of a previously introduced method. Microscopic and spectroscopic properties of the two films are related to thermal behavior induced via laser excitation of LSPR at 532 nm in the optically transparent dielectric. Gold nanoparticles were incorporated into effectively nonporous 680 μm thick polydimethylsiloxane (PDMS) films by (1) direct addition of organic-coated 16 nm nanoparticles; and (2) reduction of hydrogen tetrachloroaurate (TCA) into AuNPs. Power loss at LSPR excitation frequency and steady-state temperature maxima at 100 mW continuous laser irradiation showed corresponding increases with respect to the mass of gold introduced into the PDMS films by either method. Measured rates of temperature increase were higher for organic-coated NP, but higher gold content was achieved by reducing TCA, which resulted in larger overall temperature changes in reduced AuNP films.
Peptoids are a versatile family of oligomeric synthetic molecules that can be customized for many applications. The submonomer solid-phase synthesis of peptoids allows for quick and inexpensive manufacturing and the selection of side chains is nearly limitless. In addition, peptoids that include chiral, aromatic side chains form stable helical secondary structure that leads to the potential for the formation of supramolecular assemblies. The effects of water solubility, helical content, charge placement, and side chain bulk on microsphere formation were studied for seven peptoid sequences. We found that secondary structure and partial water solubility were essential for microsphere formation. In addition, charge placement and side chain bulk affect both the ability to form microspheres and the diameter of the microspheres.
Lattices of plasmonic nanorings with particular geometries exhibit singular, tunable resonance features in the infrared. This work examined effects of nanoring inner radius, wall thickness, and lattice constant on the spectral response of single nanorings and in Fano resonant square lattices, combining use of the discrete and coupled dipole approximations. Increasing nanoring inner radius red-shifted and broadened the localized surface plasmon resonance (LSPR), while wall thickness modulated the LSPR wavelength and decreased absorption relative to scattering. The square lattice constant was tuned to observe diffractively-coupled lattice resonances, which increased resonant extinction 4.3-fold over the single-ring LSPR through Fano resonance. Refractive index sensitivities of 760 and 1075 nm RIU(-1) were computed for the plasmon and lattice resonances of an optimized nanoring lattice. Sensitivity of an optimal nanoring lattice to a local change in dielectric, useful for sensing applications, was 4 to 5 times higher than for isolated nanorings or non-coupling arrays. This was attributable to the Fano line-shape in far-field diffractive coupling with near-field LSPR.
Gold nanoparticle arrays created with electroless gold plating provide a unique means of transforming nanocylinders usually formed in electron beam lithography to spherical nanoparticles. Alone, electroless gold plating is not selective to the substrate and results in the formation of a gold film on all exposed surfaces of an electron beam patterned sample, including the electron resist. Undesired gold plating occurred near patterned features on the substrate surface, which was reduced by increasing post-spin-coat cure time. When the electron resist is removed, some nanocylinders break off with the gold film, leaving partial cylinders or holes in the patterned elements. By presensitizing the substrate surface with tin, gold cylinders may be selectively deposited to the substrate surface without forming a film on the electron resist. Tin presensitized arrays were produced with 47.1 +/- 7.4 nm radius gold nanoparticles with an interparticle distance of 646.0 +/- 12.4 nm. Defects from sheared, missing, and redeposited Au particles associated with the resist removal were minimized, resulting in enhanced size and shape uniformity of pillars and arrays. Hollow particles were eliminated, and relative standard deviation in particle size was reduced by 7.4% on average, while elongation was reduced 12.3% when astigmatism was eliminated.
Coupling and extinction of light among particles representable as point dipoles can be characterized using the coupled dipole approximation (CDA). The analytic form for dipole polarizability of spheroidal particles supports rapid electrodynamic analysis of nanoparticle lattices using CDA. However, computational expense increases for complex shapes with non-analytical polarizabilities which require discrete dipole (DDA) or higher order approximations. This work shows fast CDA analysis of assembled nanorings is possible using a single dipole nanoring polarizability extrapolated from a DDA calculation by summing contributions from individual polarizable volume elements. Plasmon resonance wavelengths of nanorings obtained using extracted polarizabilities blueshift as wall dimensions-to-inner radius aspect ratio increases, consistent with published theory and experiment. Calculated far-field Fano resonance energy maximum and minimum wavelengths were within 1% of full volume element results. Considering polarizability allows a more complete physical picture of predicting plasmon resonance location than metal dielectric alone. This method reduces time required for calculation of diffractive coupling more than 40 000-fold in ordered nanoring systems for 400–1400 nm incident wavelengths. Extension of this technique beyond nanorings is possible for more complex shapes that exhibit dipolar or quadrupole radiation patterns.
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