Perovskite solar cells (PSCs) based on organic–inorganic hybrid materials are a rising technology offering an alternative to silicon‐based solar cells. Electron‐transport materials (ETMs) are important for PSCs and have received much attention. Here, first, the development of the structure of PSCs, from which the ETM requirements would be derived, is briefly discussed. Second, the progress of ETMs in mesoscopic PSCs, as well as regular (n–i–p) and inverted (p–i–n) planar PSCs is surveyed and analyzed, in terms of the material requirements, inorganic ETMs, organic ETMs, and interfacial materials. Third, the advancement of PSCs without ETMs is discussed. Finally, a summary and outlook on the current challenges and future development of ETMs in PSCs is given.

Organic-inorganic lead halide perovskite solar cells (PVSCs), as a competing technology with traditional inorganic solar cells, have now realized a high power conversion efficiency (PCE) of 22.1%. In PVSCs, interfacial carrier recombination is one of the dominant energy-loss mechanisms, which also results in the simultaneous loss of potential efficiency. In this work, for planar inverted PVSCs, the carrier recombination is dominated by the dopant concentration in the p-doped hole transport layers (HTLs), since the F4-TCNQ dopant induces more charge traps and electronic transmission channels, thus leading to a decrease in open-circuit voltages (V ). This issue is efficiently overcome by inserting a thin insulating polymer layer (poly(methyl methacrylate) or polystyrene) as a passivation layer with an appropriate thickness, which allows for increases in the V without significantly sacrificing the fill factor. It is believed that the passivation layer attributes to the passivation of interfacial recombination and the suppression of current leakage at the perovskite/HTL interface. By manipulating this interfacial passivation technique, a high PCE of 20.3% is achieved without hysteresis. Consequently, this versatile interfacial passivation methodology is highly useful for further improving the performance of planar inverted PVSCs.

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Organic solvent vapor introduced during the formation of hybrid perovskite films changes the grain orientation and reduces charge recombination.