Trade-Off Break between the Crystallinity and Phase Separation of Donor/Acceptor via a General Two-Dimensional Transition-Metal Phosphorus Trichalcogenides Nanoparticle Dopant Concept for Efficient and Stable All-Polymer Solar Cells

All-polymer solar cells (all-PSCs) demonstrate splendid advantages of thermal and mechanical stability. Nevertheless, the rock-ribbed trade-off between the crystallinity and phase separation scale of donor/acceptor (D/A) hinder the power conversion efficiency (PCE) improvement of all-PSCs. Here, a novel two-dimensional transition-metal phosphorus trichalcogenides (TMPTCs) namely Cd0.85PS3Li0.3 is intelligently designed and synthesized, and firstly employed as a nanoparticle dopant for PBDB-T:N2200-based all-PSCs. The two-dimensional Cd0.85PS3Li0.3 possess enormous surface area that can serve as the nucleation center, inducing the crystallinity of D/A without influencing the original phase separation. Such feature significantly boosted the charge transport, PCE (from 7.18% to 8.79%) and stability of PBDB-T:N2200-based device. Moreover, the Cd0.85PS3Li0.3 nanoparticle dopant was proved to be universal in non-fullerene small molecule acceptor (NFSMA)-based organic solar cells (OSCs), for which the PCE was boosted from 15.05% to 17.27% for PM6:L8-BO-based OSCs and from 17.29% to 19.10% for D18:L8-BO-based OSCs. These observations exemplify the significance of two-dimensional TMPTCs nanoparticle dopant as a tool for breaking the rock-ribbed trade-off between the crystallinity and phase separation scale of D/A in OSCs, which may open up a special field for making two-dimensional TMPTCs work in a unprecedented way in OSCs. Cd0.85PS3Li0.3 was added to active layer to break the trade-off between the crystallinity and phase separation of donor/acceptor, thus boosting the charge transport and power conversion efficiency of heterosystematic organic solar cellsallinity of donor/acceptor (D/A) without influencing the original phase separation, increase the charge transport of the PBDB-T:N2200 device, thus effectively restraining the charge recombination of the device. As a result, the power conversion efficiency (PCE) was boosted from 7.18% to 8.79%, for organic solar cells (OSCs) based on PBDB-T:N2200, from 15.05% to 17.27% for OSCs based on PM6:L8-BO and from 17.29% to 19.10% for OSCs based on D18:L8-BO.image (c) 2024 WILEY-VCH GmbH