A surface-enhanced Raman spectroscopy sensing template consisting of gold-covered nanopillars is developed. The plasmonic slab consists of a perforated gold film at the base of the nanopillars and a Babinet complementary dot array on top of the pillars. The nanopillars were fabricated by the incorporation of an iron salt precursor into a self-assembled block copolymer thin film and subsequent reactive ion etching. The preparation is easy, scalable, and cost-effective. We report on the increase in surfaceenhanced Raman scattering efficiency for smaller pillar heights and stronger coupling between the dot array and perforated gold film with average enhancement factors as high as 10 7 . In addition, the block copolymer-derived templates show an excellent relative standard deviation of 8% in the measurement of the Raman intensity. Finite difference time domain simulations were performed to investigate the nature of the electromagnetic near-field enhancement and to identify plasmonic hot spots.
A plasmonic structure with transmission highly tunable in the mid-infrared spectral range is developed. This structure consists of a hexagonal array of metallic discs located on top of silicon pillars protruding through holes in a metallic Babinet complementary film. We reveal with FDTD simulations that changing the hole diameter tunes the main plasmonic resonance frequency of this structure throughout the infrared range. Due to the underlying Babinet physics of these coupled arrays, the spectral width of these plasmonic resonances is strongly reduced, and the higher harmonics are suppressed. Furthermore, we demonstrate that this structure can be easily produced by a combination of the nanosphere lithography and the metal-assisted chemical etching technique.
A platform is introduced for fabrication of a reusable and highly efficient low band gap photocatalyst by confining gold nanoparticles (AuNPs) in the pores of a nanopatterned Si monolith (AuNSM). Due to their size, a maximum of two AuNPs can assemble in a single pore, thus preventing agglomerations. Their access to the analyte provides more active sites for redox reaction, leading to enhanced efficiency. While proximity of nanoparticles enhances coupling efficiency, confinement prevents rapid recombination of photogenerated charge carriers, a major factor contributing to low efficiency of photocatalytic materials. Degradation of methyl orange (MO) is used to determine the photocatalytic efficacy of AuNSM compared to 1) bare silicon and 2) AuNPs randomly dispersed on silicon. After 90 min of exposure to UV light (λ = 353 nm) in the AuNSM, the MO absorption is <1%, indicating near complete degradation, while it is still 85% and 70% for systems (1) and (2), respectively. Finite element method simulations of the confined structure suggest that the AuNPs act as a mediator/receptacle for photogenerated charges rather than a source of them at this wavelength and thus enhance the performance of the photocatalyst by creating more effective Schottky junctions—preventing recombination of electrons and holes—rather than by a localized surface plasmonic resonance effect.
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