Abstract

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.

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