Formation of Gold Nanorods by Seeded Growth: Mechanisms and Modeling

Seeded growth is one of the most successful and well-studied methods of making nanorods of face-centered cubic (FCC) metals such as Ag, Au, Pt, etc. In this method separately prepared tiny metal seeds (typically smaller than 10 nm) are added to a growth solution containing metal precursor, a weak reducing agent such as ascorbic acid, and a capping agent. The mechanisms that lead to specific shape selection and growth of nanoparticles, in this method, are poorly understood. We propose a mechanism of nanorod growth based on the physical phenomenon of twinning and develop a population balance based model. Briefly, on mixing with growth solution, the seeds start growing isotropically, during which some of the seeds undergo twinning and transform their growth habit to form nanorod nuclei. The nanorod nuclei grow along one dimension to form nanorods, and a mixture of nanorods and nanospheres is obtained after a short aging time (typically < 3 h). The simulations capture the salient features of one-dimensional growth of nanorods, along with the kinetics. The trends in experimental data are reproduced well by this model, and we are able to predict the yield of nanorods. Simulations also reveal that the growth of nanospheres competes with the nucleation and growth of nanorods; their relative magnitudes decide the yield of specific shapes in the system. The model is quite general and will apply to the seeded growth of nanorods of any material that has an FCC crystal structure.