Improving the heterointerface in hybrid organic–inorganic perovskite solar cells by surface engineering: Insights from periodic hybrid density functional theory calculations

Abstract A periodic hybrid density functional theory computational strategy is presented to model the heterointerface between the methylammonium lead iodide (MAPI) perovskite and titanium dioxide (TiO 2 ), as found in perovskite solar cells (PSC), where the 4‐chlorobenzoic acid (CBA) ligand is used to improve the stability and the band alignment at the interface. The CBA ligand acts as a bifunctional linker to efficiently connect the perovskite and the oxide moieties, ensuring the stability of the interface through Ti–O and Pb–Cl interactions. The computed density of states reveals that the perovskite contributes to the top of the valence band while the oxide contributes to the bottom of the conduction band with a direct bandgap of 2.16 eV, indicating a possible electron transfer from MAPI to TiO 2 . Dipole moment analysis additionally reveals that the CBA ligand can induce a favorable effect to improve band alignment and thus electron transfer from MAPI to TiO 2 . This latter has been quantified by calculation of the spin density of the reduced MAPI/CBA/TiO 2 system and indicates an almost quantitative (99.94%) electron transfer from MAPI to TiO 2 for the surface engineered system, together with an ultrafast electron injection time in the femtosecond timescale. Overall, the proposed DFT‐based computational protocol therefore indicates that surface engineering and the use of a bifunctional linker can lead to a better stability, together with improved band alignment and electron injection in PSC systems.