Controlling nucleation and growth in colloidal crystals using DNA

Colloidal crystal engineering with DNA has advanced beyond controlling the lattice symmetry and parameters of ordered crystals to now tuning crystal habit and size. However, the predominately used slow-cooling procedure that enables faceted crystal habits also limits control over crystal size and uniformity because nucleation and growth cannot be separated. Here, we explore how DNA sequence design can be used to deliberately separate nucleation and growth in a given crystallization process. Specifically, two batches of complementary particles are created with one batch exhibiting perfect base pair complementary while the other has a strategically introduced mismatch. This design enables the weaker binding “growth” particles to participate in heterogeneous growth on the nucleates formed from the stronger binding “seed” particles, effectively eliminating secondary nucleation pathways. By eliminating secondary nucleation events, this approach improves crystal uniformity, as measured by polydispersity (from PDI = 0.194 to 0.119), and grants control over crystal size (300 to 600 nm major axis). By using this approach with two different particle cores (gold and silver), we show how core-shell colloidal crystals can be synthesized in one-pot fashion. This work shows how tuning DNA interaction strength can profoundly impact crystal size, uniformity, and structure, parameters central to using such structures as device components.