Size-dependent growth dynamics of silver-gold core-shell nanoparticles monitored by in situ second harmonic generation and extinction spectroscopy.

The in situ growth dynamics of colloidal silver-gold core-shell (Ag@Au CS) nanoparticles (NPs) are studied using time-dependent second harmonic generation (SHG) and extinction spectroscopy. Four sequential additions of chloroauric acid, sodium citrate, and hydroquinone are added to a silver nanoparticle solution to form a gold shell around a 45 nm silver core under different reaction conditions, resulting in final sizes ranging from 80 to 125 nm in diameter. In the first addition, a bumpy, urchin-like surface morphology is produced, while the second, third, and fourth additions provide additional nanoparticle growth with the surface morphology becoming more smooth and uniform, as shown using transmission electron microscopy measurements. The in situ extinction spectra increase in intensity for each addition, where blue-shifting and spectral narrowing are observed as the Ag@Au CS NPs grow in size. The extinction spectra are compared to Mie theory simulations, showing general agreement at later stages of the reactions for smooth CS surfaces. The in situ SHG signal is dominated by surface-enhanced plasmonic hotspots at the early stages of the shell growth, followed by gradual decreases in signal as the surface becomes more smooth. Two-photon fluorescence is also monitored during the CS growth, showing complementary information for comparisons to the extinction and SHG results. The holistic study of the synthesis and characterization of Ag@Au CS nanoparticles using in situ SHG spectroscopy, extinction spectroscopy, and Mie theory simulations allows for a comprehensive analysis of the complex growth dynamics occurring at the nanoscale for developing optimized plasmonic nanomaterial properties.