Donor–Acceptor Charge‐Selective Materials for High‐Performance Perovskite Solar Cells: Molecular Design, Structure–Property Correlation and Device Performance

ABSTRACT Perovskite solar cells (PSCs) hold significant promise as the next‐generation photovoltaic technology with the certified power conversion efficiency already surpassing 27%. To further enhance device stability to meet industrial demands, it is crucial to develop high‐performance charge‐selective materials (CSMs) as they profoundly affect interfacial charge carrier dynamics and the stability of interface structure. Conventional organic CSMs often employ building blocks with a single electronic effect (e.g., using electron‐donating units to construct hole‐selective materials (HSMs) and electron‐withdrawing groups to develop electron‐selective materials (ESMs)), which usually face the dilemma that high charge transport ability, superior film morphology, and strong interfacial functionality cannot be achieved simultaneously. In contrast, donor(D)–acceptor(A) CSMs allow more precise tuning of molecular structure, aggregation behavior, electronic properties, and interfacial functionalities, thus providing an ideal design platform for exploration of efficient CSMs. Therefore, this review timely summarizes the progress of D–A type CSMs, covering both HSMs and ESMs. Specifically, we will deeply explore the relationships between molecular structures and material properties, as well as their effects on device performance and stability. Finally, future research directions in material design are proposed to advance the industrialization of PSCs.