Impact of Electrostatic Interaction on Vertical Morphology and Energy Loss in Efficient Pseudo‐Planar Heterojunction Organic Solar Cells

Abstract Although a suitable vertical phase separation (VPS) morphology is essential for improving charge transport efficiency, reducing charge recombination, and ultimately boosting the efficiency of organic solar cells (OSCs), there is a lack of theoretical guidance on how to achieve the ideal morphology. Herein, a relationship between the molecular structure and the VPS morphology of pseudo‐planar heterojunction (PPHJ) OSCs is established by using molecular surface electrostatic potential (ESP) as a bridge. The morphological evolution mechanism is revealed by studying four binary systems with vary electrostatic potential difference (∆ESP) between donors (Ds) and acceptors (As). The findings manifest that as ∆ESP increases, the active layer is more likely to form a well‐mixed phase, while a smaller ∆ESP favors VPS morphology. Interestingly, it is also observed that a larger ∆ESP leads to enhanced miscibility between Ds and As, resulting in higher non‐radiative energy losses (ΔE₃). Based on these discoveries, a ternary PPHJ device is meticulously designed with an appropriate ∆ESP to obtain better VPS morphology and lower ΔE₃, and an impressive efficiency of 19.09% is achieved. This work demonstrates that by optimizing the ΔESP, not only the formation of VPS morphology can be controlled, but also energy losses can be reduced, paving the way to further boost OSC performance.