Regulating molecular stacking to construct a superior interfacial contact for highly efficient and stable perovskite solar cells.

• Interfacial molecular stacking is optimized by a symmetric DDS molecule. • The DDS exhibits defect passivation capability and hydrophobicity. • A suitable intermediate energy level is achieved by DDS modification at the interface. • Carrier transfer and extraction are promoted by the DDS interlayer. • The PCE increases from 21.05% to 24.02% with a high fill factor of 84.0%. The non-radiative charge carrier recombination loss at the surface and interface of the perovskite layers in perovskite solar cells (PSCs) is the main cause of their limited power conversion efficiency (PCE). Here we propose an efficient strategy to minimize the non-radiative recombination by introducing symmetric molecules with regular arrangement at the interface between the perovskite layer and hole transport layer (HTL). One end of the symmetric molecule gets in a close contact with the terminal groups of the molecules in the HTL, while the other end promotes connection with the perovskite, resulting in an enhanced interfacial electrical contact and a better valence band energy-level alignment for efficient hole extraction. In contrast, introducing similar but asymmetrical molecules forms a dimer structure and mismatched energy levels at the interface region, which is detrimental to the carrier transport. The best-performing planar PSC with the symmetric molecular modification exhibited an increase in the PCE from 21.05% to 24.02% with a substantially enhanced fill factor of 84.0%, which can be ascribed to the synergistic effects of surface defect passivation and reduction in the interfacial energy barrier. Furthermore, the corresponding unencapsulated PSC retained 80% of the original PCE after 4,000 h of aging in dry air. [ABSTRACT FROM AUTHOR]