Charge Carrier Dynamics at the Interface of 2D Metal–Organic Frameworks and Hybrid Perovskites for Solar Energy Harvesting

Interfacing perovskites with two-dimensional materials such as metal–organic frameworks (MOFs) for improved stability and electron or hole extraction has emerged as a promising path forward for the generation of highly efficient and stable solar cells. In this work, we examine the structural properties and excitation dynamics of two MOF–perovskite systems: UMCM309-a@MAPbI₃ and ZrL3@MAPbI₃. We find that precise band alignment and electronegativity of the MOF-linkers are necessary to facilitate the capture of excited charge carriers. Furthermore, we demonstrate that intraband relaxation of hot electrons to the MOF subsystem results in optically disallowed transitions across the band gap, suppressing radiative recombination. Furthermore, we elucidate the key mechanisms associated with improved structural stability afforded to the perovskites by the two-dimensional MOFs, highlighting the necessity of broad surface coverage and strong MOF–perovskite interaction.