Formation of bimetallic dumbbell shaped particles with a hollow junction during galvanic replacement reaction

The galvanic replacement reaction (GRR) has been shown to be an effective method to fine tune the structure of monometallic nanoparticles by controlling the precursor concentration and surface ligands. However, the structural evolution of nanoparticles is not well understood in multimetallic systems, where along with oxidation, dealloying and diffusion occur simultaneously. Here, we demonstrate that by controlling the rate of GRR in AuCu alloy nanorods, they can be transformed into either AuCu hollow rods or AuCu@Au core-shell spheroids. Interestingly, the transformation of rods into spheroids involved a critical intermediate state with a hollow junction and dumbbell shape. The formation of a hollow junction region was attributed to preferential diffusion of Cu atoms to the tips caused by the polycrystallinity and high curvature of the tips of the initial template. This structural transformation was also monitored in situ by single particle scattering spectroscopy. The coupling between the two ends of the dumbbell-shaped intermediate connected with a hollow metallic junction gives rise to additional plasmonic features compared with regular rods. Electrodynamic simulations showed that varying the dimensions of the hollow part by even one nanometer altered the plasmon resonance wavelength and lineshape drastically. This study shows that single particle plasmon resonance can be used as an exquisite tool to probe the internal structure of the nanoscale junctions.