Nanoparticle Heat-Up Synthesis: In Situ X-ray Diffraction and Extension from Classical to Nonclassical Nucleation and...

Heat-up synthesis routes are very commonly used for the controlled large-scale production of semiconductor and magnetic nanoparticles with narrow size distribution and high crystallinity. To obtain fundamental insights into the nucleation and growth kinetics is particularly demanding, because these procedures involve heating to temperatures above 300 °C. We designed a sample environment to perform in situ SAXS/WAXS experiments to investigate the nucleation and growth kinetics of iron oxide nanoparticles during heat-up synthesis up to 320 °C. The analysis of the growth curves for varying heating rates, Fe/ligand ratios, and plateau temperatures shows that the kinetics proceeds via a characteristic sequence of three phases: an induction Phase I, a final growth Phase III, and an intermediate Phase II, which can be divided into an early phase with the evolution and subsequent dissolution of an amorphous transient state, and a late phase, where crystalline particle nucleation and aggregation occurs. We extended classical nucleation and growth theory to account for an amorphous transient state and particle aggregation during the nucleation and growth phases. We find that this nonclassical theory is able to quantitatively describe all measured growth curves. The model provides fundamental insights into the underlying kinetic processes especially in the complex Phase II with the occurrence of a transient amorphous state, the nucleation of crystalline primary particles, particle growth, and particle aggregation proceeding on overlapping time scales. The described in situ experiments together with the extension of the classical nucleation and growth model highlight the two most important features of nonclassical nucleation and growth routes, i.e., the formation of intermediate or transient species and particle aggregation processes. They thus allow us to quantitatively understand, predict, and control nanoparticle nucleation and growth kinetics for a wide range of nanoparticle systems and synthetic procedures.