Heterojunction Aggregation in Organic Electronics: From Performance Optimization to Multifunctional Applications

ABSTRACT Organic electronic devices offer unique advantages in flexible, solution‐processable, and cost‐effective applications, where molecular stacking directly determines the optoelectronic properties of materials and devices. Heterojunction microstructures, which serve as the fundamental building blocks for controlling photoexciton dynamics and charge transport processes, have emerged as a critical feature to govern the coordination of exciton dynamics, charge transport, and multifunctional coupling in organic semiconductors. In this review, we provide a comprehensive overview of recent advances in heterojunction microstructures for modulating optoelectronic properties, offering valuable insights for high‐performance and multifunctional organic electronics applications. We begin by introducing the fundamentals of heterojunction aggregation and its role in modulating physical processes through electronic structure and carrier transport engineering. Subsequently, we review recent progress in heterojunction aggregation within organic electronics, encompassing performance optimization and multifunctional extensions. In addition, we summarize four key strategies for constructing heterojunction microstructures in organic electronic devices. Finally, we outline future perspectives, emphasizing the critical need for deeper understanding of aggregation dynamics and the development of scalable fabrication approaches for heterojunction‐structured films in next‐generation intelligent devices.