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 Cd 0.85 PS 3 Li 0.3 is intelligently designed and synthesized, and firstly employed as a nanoparticle dopant for PBDB-T:N2200-based all-PSCs. The two-dimensional Cd 0.85 PS 3 Li 0.3 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 Cd 0.85 PS 3 Li 0.3 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.