Simple hybrid dithiafulvenes-triphenylamine systems as dopant-free hole-transporting materials for efficient perovskite solar cells

Two extended hybrid conjugated systems based on a triphenylamine(TPA) core with two and three peripheral 1,4-dithiafulvenes(DTF) units coded WH-2 and WH-3 as hole-transporting materials(HTMs) applied in perovskite solar cells(PSCs) are synthesized by facile one-step reaction in good yield over 75%. DTF unit as electron donor can enhance the electron donating ability and the fusion of benzenic ring of TPA with DTF unit may lead to reinforced intermolecular interactions in the solid state. In addition,WH-2 and WH-3 exhibit a pyramid shape containing partial planarity and quasi three-dimensionality features, which is also conducive to enhancing the π-π stacking of molecules in the solid state. The above-mentioned structural characteristics make the two HTMs have good hole mobilities. As a result,WH-2 and WH-3 obtained the high intrinsic hole mobilities of 4.69 × 10^(-4)and 2.18 × 10^(-3)cm^(2)V^(-1)s^(-1)respectively. Finally, the power conversion efficiencies(PCEs) of PSCs with WH-2 and WH-3 as cost-effective dopant-free HTMs are 15.39% and 19.22% respectively and the PCE of PSC with WH-3 is on a par with that of PSC with Li-TFSI/t-BP doped Spiro-OMe TAD(19.67%).

Chelation of lithium ion with crown ether for eliminating adverse effects caused by Li-TFSI/tBP doping system in Spiro-OMeTAD

Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI)/4-tert-butylpyridine(tBP)is a classic doping system for the hole transport material Spiro-OMeTAD in typical n-i-p structure perovskite solar cells(PSCs),but this system will cause many problems such as high hygroscopicity,Li+migration,pinholes and so on,which hinder PSC from maintaining high efficiency and stability for long-term.In this work,an effective strategy is demonstrated to improve the performance and stability of PSC by replacing t BP with 12-crown-4.The chelation of 12-crown-4 with Li+not only improves the doping effect of Li-TFSI,but also perfectly solves the problems caused by the Li-TFSI/tBP system.The PSC based on this strategy achieved a champion power conversion efficiency(PCE)over 21%,which is significantly better than the pristine device(19.37%).More importantly,the without encapsulated device based on Li-TFSI/12-crown-4 still maintains 87%of the initial PCE even after 60 days exposure in air,while the pristine device only maintains 22%of the initial PCE under the same aging conditions.This strategy paves a novel way for constructing efficient and stable PSCs.