Phase-field simulations of the morphology formation in evaporating crystalline multicomponent films

TL;DR

This paper introduces a comprehensive phase-field simulation framework that models the complex interplay of physical mechanisms like phase separation, crystallization, and evaporation in drying multicomponent films, aiding understanding of morphology formation.

Contribution

It develops a unified theoretical model combining Cahn-Hilliard and Allen-Cahn equations coupled with fluid dynamics to simulate morphology evolution in evaporating films.

Findings

Model successfully simulates morphology formation pathways.

Framework captures effects of multiple physical mechanisms.

Application to organic photovoltaics demonstrates practical relevance.

Abstract

In numerous solution-processed thin films, a complex morphology resulting from liquid-liquid phase separation (LLPS) or from polycrystallization arises during the drying or subsequent processing steps. The morphology has a strong influence on the performance of the final device but unfortunately the process-structure relationship is often poorly and only qualitatively understood. This is because many different physical mechanisms (miscibility, evaporation, crystallization, diffusion, advection) are active at potentially different time scales, and because the kinetics plays a crucial role: the morphology develops until it is kinetically quenched far from equilibrium. In order to unravel the various possible structure formation pathways, we propose a unified theoretical framework that takes into account all these physical phenomena. This phase-field simulation tool is based on the Cahn-Hilliard equations for diffusion and the Allen-Cahn equation for crystallization and evaporation, which are coupled to the equations for the dynamics of the fluid. We discuss and verify the behavior of the coupled model based on simple test cases. Furthermore, we illustrate how this framework allows to investigate the morphology formation in a drying film undergoing evaporation-induced LLPS and crystallization, which is typically a situation encountered, e.g., in organic photovoltaics applications.