Evolution of Anisotropic Arrow Nanostructures during Controlled Overgrowth

Abstract

Anisotropic metal nanoparticles (NPs), such as high‐aspect‐ratio Au nanorods (NRs), play an important role for applications in photocatalysis, sensing, and drug delivery because of their adjustable plasmon resonances. Their performance for these applications can be further improved by fine‐tuning their morphologies. Achieving desired NP architectures requires insight into their formation mechanisms. Here, liquid‐phase transmission electron microscopy is used to directly follow the overgrowth of Au NR seeds into nanoarrows (NAs) with fourfold symmetric wings along the sides. Adding thiol molecules like L‐cysteine to the growth solution can lead to the formation of NAs with periodic prismatic teeth instead of the straight side wings. These observations suggest that this transition is controlled by binding of L‐cysteine to the NR surface, which in turn, slows down the metal deposition rate, switching the overgrowth from the kinetically to thermodynamically controlled process. Furthermore, simulations demonstrate that these prismatic teeth enhance the NPs’ plasmonic properties. The study describes how thiol additives control the morphological evolution of metal NPs, which is important for the fabrication of NPs with tailored shapes for a broad range of applications.