Luminescent silicon nanocrystals are promising nanomaterials for biomedical applications due to their unique optical properties and biocompatibility. Here, we demonstrate a two-step surface modification approach coupling gas-phase and liquid-phase methods to synthesize PEGylated acrylic acid grafted silicon nanocrystals with near-infrared emission in water and biological media. First, acrylic acid grafted silicon nanocrystals are synthesized by an all-gas-phase approach on a millisecond time scale, omitting high temperature and postpurification processes. Subsequently, room-temperature PEGylation is carried out with these acrylic acid grafted silicon nanocrystals, yielding stable colloidal dispersions in both water and high ionic strength Tyrode’s buffer with 20–30 nm hydrodynamic diameters. The PEGylated silicon nanocrystals exhibit photoluminescence in the 650–900 nm near-IR window with quantum yields of ∼30% and ∼13% in deionized water and Tyrode’s buffer, respectively, after a 7-day oxidation in water. The surface-functionalized Si NCs exhibit relatively small toxicity to MDA-MB-231 cells at concentrations relevant to bioimaging applications.
Optically Mie-resonant crystalline silicon nanoparticles have long attracted interest for their unique scattering behaviors. Here, we report a bottom-up nonthermal plasma process that produces highly monodisperse particles, with diameters controllable between 60 and 214 nm, by temporarily electrostatically trapping nanoparticles inside a continuous-flow plasma reactor. The particle size is tuned by adjusting the gas residence time in the reactor. By dispersing the nanoparticles in water, optical extinction measurements indicate colloidal solutions of a particle-based metafluid in which particles support both strong magnetic and electric dipole resonances at visible wavelengths. The spectral overlap of the electric and magnetic resonances gives rise to directional Kerker scattering. The extinction measurements show excellent agreement with Mie theory, supporting the idea that the fabrication process enables particles with narrow distributions in size, shape, and composition. This single-step gas-phase process can also produce Mie-resonant nanoparticles of dielectric materials other than silicon and directly deposit them on the desired substrates.
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