Perovskite Crystallization Control for Large, Oriented Grains with Residual Solvent Restrain via Hydrogen‐Bonded Organic Frameworks

Abstract Void‐free perovskite films with oriented large grains are considered good performance. However, contradictory requirements on solvent volatilization arise that the growth of large grains requires slow volatilization while the residual solvent problem, which leads to difficult‐handled voids at buried interface, requires quick and complete volatilization. Currently, although grain boundary additives help reach large and oriented grains, the occupation of additives in the grain boundary volatilization channel may further deteriorate the residual solvent problem. Herein, porous structures with “switchable pore” nature are constructed based on flexible hydrogen‐bonded (HOF‐FJU‐2) in perovskite grain boundaries to meet both contradictory requirements with achieving crystallization control and residual solvent restrain. The additive molecules prolongs the perovskite crystallization through the Pb‐O bond and guides the growth of (100) facet based on its strong ordered accumulation trend. The pre‐embedded porous structure opens up the solvent volatilization channel for complete volatilization in annealing stage and then switches to a closed pore state via phase transformation after the solvent completely leaves, preventing the intrusion of the external environment. Combined with theoretical calculations and in situ spectrum tests, the crystallization thermodynamics and dynamics are analyzed. As expected, the target device exhibits enhanced performance (improved from 22.14% to 24.18%) and stability.