Role of Solid Additives in Morphological and Structural Optimization of Bulk Heterojunction Organic Solar Cells

Additive engineering has become a critical strategy for optimizing the morphology and performance of bulk heterojunction (BHJ) organic solar cells (OSCs), while volatile solid additives have been widely employed to control nanoscale phase separation during film formation. Concerns regarding reproducibility, residual solvent effects, and long-term stability have stimulated increasing interest in non-volatile solid additives. In recent years, solid additive engineering has emerged as a promising approach for modulating molecular packing, regulating phase separation, enhancing charge transport, and improving device stability. However, a systematic analysis of its material design principles and performance impact remains limited. This review summarizes recent progress in solid additive engineering for OSCs, categorizing reported additives into non-volatile, volatile and nanomaterials. The effects of these additives on key photovoltaic parameters, including open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and power conversion efficiency (PCE), are comparatively analyzed based on the reported data. Particular emphasis is placed on morphology and structural performance relationships and stability enhancement mechanisms. Finally, current challenges, including the lack of universal molecular design rules and limited mechanistic understanding of additive host interactions, are discussed, and future research directions are proposed. This review aims to provide a comprehensive perspective on the material-level role of solid additives and to guide the rational design of next-generation high-performance and stable organic solar cells.