Symmetry Making and Breaking in Seeded Syntheses of Metal Nanocrystals

Crystal growth theory predicts that heterogeneous nucleation will occur preferentially at defect sites, such as the vertices rather than the faces of shape-controlled seeds. Platonic metal solids are generally assumed to have vertices with nearly identical chemical potentials, and also nearly identical faces, leading to the useful generality that heterogeneous nucleation preserves the symmetry of the original seeds in the final product. This presentation will discuss how this generality can be used to access stellated metal nanocrystals with high and tunable symmetries for applications in plasmonics. This presentation will also discuss the limits of this generality in the extreme of low supersaturation. A strategy for favoring localized deposition that differentiates between both different vertices and different edges or faces, i.e., regioselective deposition, will be demonstrated. Such regioselective heterogeneous nucleation was achieved at low supersaturation by a kinetic preference for high-energy defect-rich sites over lower-energy sites. This outcome was enhanced by using capping agents to passivate facet sites where deposition was not desired. Collectively, the results presented provide a model for breaking the symmetry of seeded growth and for achieving regioselective deposition.

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Acknowledgements
US National Science Foundation, Division of Chemistry #1602476