Universal crystallization kinetics of solution-processed semiconductors

Abstract

Heterogeneous crystallization kinetics critically govern the morphology and performance of solution-processed semiconductors, yet morphology control is often achieved through trial-and-error optimization. Quantitative understanding of crystallization is essential for precise morphology control but is limited by the simultaneous occurrence of heterogeneous nucleation and crystal growth. Here, a time-defined induced nucleation strategy has been developed to initiate crystallization at specific stages of solution processing. Systematic variation of nucleation timing reveals three distinct morphological regimes, whose emergence is explained by the concentration-dependent critical cluster radius in bulk, interfacial, and cusp environments. On this basis, a quantitative, dimensionless model is developed for heterogeneous crystallization kinetics across diverse processing conditions. The model demonstrates universality across perovskite and organic semiconductors. In situ studies reveal identical growth kinetics for induced and spontaneous nuclei, validating its generality. The resulting morphology control enables tuning of crystallinity and charge transport in solution-processed transistors. The work establishes a universal, experimentally validated model of heterogeneous nucleation and diffusion-controlled crystallization, predicting domain growth across diverse solution-processed semiconductors for efficient charge transport.