Kinetic Exploration of Nanoscale Polymorphs through Interface Energy Adjustment.

Traditionally, the study of crystal polymorphism has relied on thermodynamics and measurements averaged over time and the crystal's constituents. This work introduces a kinetic approach to phase identification─millisecond cinematographic electron microscopic imaging of the dynamics of phase transitions of crystals of a few nm in diameter. We demonstrate a remarkable impact of the interface energy on the relative stability of the nanocrystal's polymorphs, enabling in situ manipulation of phase transitions through size increase or decrease. Starting with the B1 NaI polymorph at 298 K, we identified the previously unknown B2 polymorph of a 1 s lifetime upon sublimation of the crystal. From the CsCl liquid phase, we produced the B1 phase, previously described only at 749 K.