Synthesis of Ag Nanorods with Highly Tunable Plasmonics toward Optimal Surface‐Enhanced Raman Scattering Substrates Self‐Assembled at Interfaces

Abstract Ag nanorods receive intensive attention due to the excellent plasmonic properties. However, the difficulty in synthesis of monodisperse Ag nanorods with broad aspect ratios has limited their in‐depth applications. Here, a seed‐mediated method is reported for the synthesis of Ag nanorods with lengths from 65 to 5000 nm, corresponding to aspect ratios from 2 to 156. The plasmonic resonance is tuned from visible to mid‐infrared wavelength. The synthesis protocol relies on robust Au seeds synthesized in N,N‐dimethylformamide (DMF), which induces the one‐dimensional (1D) growth of Ag atoms. To maintain symmetry breaking initiated by the Au seeds, the reduction rate of Ag⁺ is decreased by adding hexadecyltrimethylammonium chloride (CTAC) to form AgCl particles. The optimized conditions to prevent the homogeneous nucleation of Ag nanoparticles and residue of AgCl particles in products are identified, under which the conversion efficiency of Ag ions to Ag nanorods is evaluated about 48%. More importantly, the anisotropic Ag nanorods are self‐assembled into monolayers at interfaces with the long axis of Ag nanorods perpendicular or parallel to the interfaces, respectively. The as‐fabricated monolayers exhibit uniform and reproducible surface‐enhanced Raman scattering (SERS) activities. The optimal SERS performance is achieved from Ag nanorod monolayer with vertical orientation and the longest rod length.