Understanding the Role of Removable Solid Additives: Selective Interaction Contributes to Vertical Component Distributions.

Sequentially deposited organic solar cells (SD-OSCs) have attracted great attention owing to their ability in achieving a more favorable, vertically phase-separated morphology to avoid the accumulation of counter charges at absorber/transporting layer interfaces. However, the processing of SD-OSCs is still quite challenging in preventing the penetration of small-molecule acceptors into the polymer donor layer via erosion or swelling. Herein, solid additives (SAs) with varied electrostatic potential distributions and steric hinderance are introduced into SD-OSCs to investigate the effect of evaporation dynamics and selective interaction on vertical component distribution. Multiple modelings indicate that the π-π interaction dominates the interactions between aromatic SAs and active layer components. Among them, p-dibromobenzene shows a stronger interaction with the donor while 2-chloronaphthalene (2-CN) interacts more preferably with acceptor. Combining the depth-dependent morphological study aided by multiple X-ray scattering methods, it is concluded that the evaporation of SAs can drive the stronger-interaction component upward to the surface, while having minor impact on the overall molecular packing. Ultimately, the 2-CN-treated devices with reduced acceptor concentration at the bottom surface deliver a high power conversion efficiency of 19.2%, demonstrating the effectiveness of applying selective interactions to improve the vertical morphology of OSCs by using SAs with proper structure.