Tunable plasmonic gallium nano liquid metal from facile and controllable synthesis

Abstract

Liquid metal (LM) gallium (Ga) is famous for its metallic properties with unique fluidity and has been extensively utilized in modern technologies. However, chemical strategies towards nanostructured Ga are extremely challenging, which severely limits further advanced applications of Ga. This work reports a facile method, the classical galvanic replacement reaction (GRR), to readily realize the synthesis of uniform Ga nano LM through sacrificial seeds (zinc) and gallium ions (Ga³⁺). Different from the previous tedious Ga nanoparticle synthesis, the GRR can be achieved under mild conditions without involving any highly active reagents or special equipment. Surprisingly, the temperature heavily influences the results of GRR due to the unique solid–liquid phase transition of Ga LM. This work figures out the critical issues of temperature, oxygen and solvent in the GRR to successfully prepare Ga nanodroplets. Interestingly, the GRR provides a convenient strategy to control the size of Ga nano LM to mediate localized surface plasmon resonance (LSPR) in the ultraviolet region, which is hardly observed in noble metals. Besides, the nano Ga from GRR exhibits remarkable SERS detection capability with an extremely low limit of detection (10⁻⁶ M), which ranks as the highest enhancement factor with an average value exceeding 10⁵ among Ga materials. Moreover, the SERS activity of the nano Ga shows no obvious decrease within 60 days, verifying its excellent storage stability. This work demonstrates a facile “bottom-up” chemistry for Ga LM, which could greatly benefit its potential applications in the future.