Direct Bottom-Up In Situ Growth: A Paradigm Shift for Studies in Wet-Chemical Synthesis of Gold Nanoparticles.

Plasmonic gold nanoparticles have been used increasingly in solid-state systems because of their applicability in fabricating novel sensors, heterogeneous catalysts, metamaterials, and thermoplasmonic substrates. While bottom-up colloidal syntheses take advantage of the chemical environment to control size, shape, composition, surface chemistry, and crystallography of the nanostructures precisely, it can be challenging to assemble nanoparticles rationally from suspension onto solid supports or within devices. In this Review, we discuss a powerful recent synthetic methodology, bottom-up in situ substrate growth, which circumvents time-consuming batch presynthesis, ligand exchange, and self-assembly steps by applying wet-chemical synthesis to form morphologically controlled nanostructures on supporting materials. First, we briefly introduce the properties of plasmonic nanostructures. Then we comprehensively summarize recent work that adds to the synthetic understanding of in situ geometrical and spatial control (patterning). Next, we briefly discuss applications of plasmonic hybrid materials prepared by in situ growth. Overall, despite the vast potential advantages of in situ growth, the mechanistic understanding of these methodologies remains far from established, providing opportunities and challenges for future research.

Surface Lattice Plasmon Resonances by Direct In Situ Substrate Growth of Gold Nanoparticles in Ordered Arrays.

Precise arrangements of plasmonic nanoparticles on substrates are important for designing optoelectronics, sensors and metamaterials with rational electronic, optical and magnetic properties. Bottom-up synthesis offers unmatched control over morphology and optical response of individual plasmonic building blocks. Usually, the incorporation of nanoparticles made by bottom-up wet chemistry starts from batch synthesis of colloids, which requires time-consuming and hard-to-scale steps like ligand exchange and self-assembly. Herein, an unconventional bottom-up wet-chemical synthetic approach for producing gold nanoparticle ordered arrays is developed. Water-processable hydroxypropyl cellulose stencils facilitate the patterning of a reductant chemical ink on which nanoparticle growth selectively occurs. Arrays exhibiting lattice plasmon resonances in the visible region and near infrared (quality factors of >20) are produced following a rapid synthetic step (<10 min), all without cleanroom fabrication, specialized equipment, or self-assembly, constituting a major step forward in establishing in situ growth approaches. Further, the technical capabilities of this method through modulation of the particle size, shape, and array spacings directly on the substrate are demonstrated. Ultimately, establishing a fundamental understanding of in situ growth has the potential to inform the fabrication of plasmonic materials; opening the door for in situ growth fabrication of waveguides, lasing platforms, and plasmonic sensors.

Plasmonic Metasurfaces Based on Pyramidal Nanoholes for High-Efficiency SERS Biosensing.

An inverted pyramidal metasurface was designed, fabricated, and studied at the nanoscale level for the development of a label-free pathogen detection on a chip platform that merges nanotechnology and surface-enhanced Raman scattering (SERS). Based on the integration and synergy of these ingredients, a virus immunoassay was proposed as a relevant proof of concept for very sensitive detection of hepatitis A virus, for the first time to our best knowledge, in a very small volume (2 µL), without complex signal amplification, allowing to detect a minimal virus concentration of 13 pg/mL. The proposed work aims to develop a high-flux and high-accuracy surface-enhanced Raman spectroscopy (SERS) nanobiosensor for the detection of pathogens to provide an effective method for early and easy water monitoring, which can be fast and convenient.