Promotion Strategies of Hole Transport Materials by Electronic and Steric Controls for n–i–p Perovskite Solar Cells

Abstract Hole transport materials (HTMs) play a requisite role in n–i–p perovskite solar cells (PSCs). The properties of HTMs, such as hole extraction efficiency, chemical compatibility, film morphology, ion migration barrier, and so on, significantly affect PSCs’ power conversion efficiencies (PCEs) and stabilities. Up till now, researchers have devoted much attention to developing new types of HTMs as well as promoting pristine HTMs using numerous strategies. In this Review, we summarize the design strategies of various common HTMs for n–i–p PSCs are comprehensively discussed from two separate aspects (additive and non‐additive engineering). Additive engineering generally tunes electronic properties of HTMs while non‐additive engineering basically modifies their steric structures. Critical analysis and comparison between these design strategies are provided, considering the overall PCEs and stabilities of PSCs. Finally, a brief perspective on future promising design strategies for HTMs is given, in order to fabricate efficient and stable n–i–p devices for the commercialization of PSCs.