Multi-Step Crystallization and Chemical Evolution of Sodium Yttrium Fluoride

Abstract Two-step crystallization mechanisms based on spinodal decomposition followed by nucleation are commonly observed both in the laboratory and in nature. While this pathway may require chemical reactions, subsequent nucleation and growth are often considered as separate, discrete events from the reaction itself. Recent work has also shown a distinct intermediate step involving the formation of an amorphous aggregate. Here we report a novel four-step mechanism in the aqueous synthesis of sodium yttrium fluoride involving 1) the segregation of aqueous ions into a dense liquid phase, 2) the formation of an amorphous aggregate, 3) nucleation of a cubic YF3 phase, and 4) subsequent solid-state diffusion of sodium and fluoride ions to form a final NaYF4 phase. The final step involves a continuous, gradual change of the solid phase’s chemical stoichiometry from YF3 toward NaYF4. Unlike previously studied nucleation and growth mechanisms, the stoichiometry of the final solid phase evolves throughout the crystallization process rather than being determined at nucleation. This novel four-step mechanism provides a new perspective into the nucleation and growth of many other crystalline materials given the ubiquity of nonstoichiometric compounds in nature.