Fused Dithienopicenocarbazole Enabling High Mobility Dopant-Free Hole-Transporting Polymers for Efficient and Stable...

As a critical component in perovskite solar cells (PSCs), hole-transporting materials (HTMs) have been extensively explored. To develop efficient dopant-free HTMs for PSCs, a decent hole mobility (>10^-3 cm² V^-1 s^-1) is critically essential, which is, however, seldom reported. In this work, we introduce two novel donor-acceptor (D-A) type conjugated polymers (PDTPC-1 and PDTPC-2) with narrow bandgap unit, i.e., fused dithienopicenocarbazole (DTPC), as the donor building block and benzo[c][1,2,5]thiadiazole derivatives as the acceptors. The highly planar and strong electron-donating DTPC endows the polymers with superior hole mobility up to ∼4 × 10^-3 cm² V^-1 s^-1. Because of the better energy alignment with perovskite and excellent film-forming property, PSCs with PDTPC-1 as HTM show an appreciably enhanced PCE of ∼17% in dopant-free PSCs along with improved device stability as opposed to PDTPC-2. Our work revealed for the first time that the introduction of narrow bandgap DTPC in D-A polymers could achieve remarkably high hole mobility in the pristine form, favoring the application in dopant-free PSCs.