Casting of a donor:acceptor bulk-heterojunction structure from a single ink has been the predominant fabrication method of solution-processed organic photovoltaics (OPVs). Despite the success of such bulk-heterojunction, the task of controlling its microstructure in a single casting process has been challenging and arduous and alternative approaches are desired. To achieve and even improve OPVs with a desirable microstructure, a facile and eco-compatible sequential deposition approach is demonstrated for nonfullerene polymer/small molecule pairs. Using a known weakly crystalline polymer FTAZ as the model material, we show the profound influence of casting solvent on the molecular ordering of the film, and thus the device performance and mesoscale morphology of sequentially deposited OPVs can be tuned. Static and in-situ X-ray scattering indicate that applying the green solvent limonene is able to greatly promote the molecular order of FTAZ and form the largest domain spacing exclusively, which correlate well with the best efficiency in sequentially deposited devices. The sequentially cast device generally outperforms its control device based on traditional single-ink bulk-heterojunction structure. Investigations of distinct material systems suggest that our approach be applicable to many conjugated polymers and nonfullerene acceptors, which yield consistently higher fill factors than traditional bulk-heterojunction devices. Moreover, the relationships between polymer:solvent interactions, thin-film microstructure, and device performance are discussed for these sequentially deposited devices. It is noted that polymer:solvent interaction parameter χ positively correlates with domain spacing in the devices. Our findings shed light on innovative approaches to rationally create ink-stable, environmentally friendly, and highly efficient nonfullerene solar cells.
 Ye, L.; Xiong, Y.; Chen, Z.; Zhang, Q.; Fei, Z.; Henry, R.; Heeney, M.; O’Connor, B.; You, W.; Ade, H. Adv. Mater. 2019, under review.
 Ye, L.; Xiong, Y.; Zhang, Q.; Li, S.; Wang, C.; Jiang, Z.; Hou, J.; You, W.; Ade, H. Adv. Mater. 2018, DOI: 10.1002/adma.201705485.