Mesostructured arrays of nanometer-spaced gold nanoparticles for ultrahigh number density of SERS hot spots

A novel one-trough synthesis via an air-water interface is demonstrated to provide hexagonally packed arrays of densely spaced metallic nanoparticles (NPs). In the synthesis, a mesostructured polyoxometalate (POM)-silicatropic template (PSS) is first self-assembled at the air-water interface; upon UV irradiation, anion exchange cycles enable the free-floating PSS film to continuously uptake gold precursors from the solution subphase for diffusion-controlled and POM-site-directed photoreduction inside the silica channels. NPs ≈ 2 nm can hence be homogeneously formed inside the silica-surfactant channels until saturation. As revealed via X-ray diffraction, small-angle X-ray scattering (SAXS), grazing incidence SAXS, and transmission electron microscopy, the Au NPs directed by the PSS template are arrayed into a 2D hexagonal lattice with inter-channel spacing of 3.2 nm and a mean along-channel NP spacing of 2.8 nm. This corresponds to an ultra-high number density (≈10¹⁹ NPs cm^-3) of narrowly spaced Au NPs in the Au-NP@PSS composite, leading to 3D densely deployed hot-spots along and across the mesostructured POM-silica channels for surface-enhanced Raman scattering (SERS). Consequently, the Au-NP@PSS composite exhibits prominent SERS with 4-mercaptobenzoic acid (4-MBA) adsorbed onto Au NPs. The best 4-MBA detection limit is 5 nm, with corresponding SERS enhancement factors above 10⁸. Densely arrayed metallic nanoparticles are fabricated via self-assembly of a mesostructured polyoxometalate-silicate-surfactant (PSS) template at the air-water interface (left), followed by adsorption of metallic precursors to the PSS film via anion exchange (middle), then finished by polyoxometalate (POM)-site-directed photoreduction of the metallic anions and formation of metallic NPs inside the silicate-surfactant channels upon UV irradiation (right).