Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) are expected to be a viable alternative to three-dimensional (3D) analogs in solar cells (SCs) and optoelectronic devices due to their high stability, diverse composition, and physical properties. However, unsuitable band alignment and large bandgaps limit the power conversion efficiency (PCE) improvement of SCs based on 2D HOIPs. Here, we report a molecular design strategy that combines fluorination and conjugation engineering to tune the electronic structure and optimize the PCE of 2D HOIPs. Our results show that type IIa band alignment and tunable bandgaps can be achieved in 2D Dion-Jacobson (DJ) HOIPs by H/F substitution of organic cations with different degrees of conjugation. In general, the bandgap of 2D DJ-HOIPs decreases monotonously with the increase of the number of F atoms, which is due to the gradual decrease of the lowest unoccupied molecular orbitals (LUMO) of organic cations. In addition, the enhanced interlayer charge transfer and higher dielectric constant suggest that the fluorination-induced dielectric limitations are weakened. The estimated PCE of 2D DJ-HOIPs is exponentially increased and positively correlated with the degree of conjugation and fluorination of organic cations, with a PCE approaching 29% under their synergistic effect. Our results not only provide promising candidates for photovoltaic device applications but also provide an effective method for PCE optimization.
Keywords: conjugation engineering; first-principles; fluorination; power conversion efficiency; two-dimensional perovskites.