LAUSR

The rational design of dopant-free organic hole-transporting layer (HTL) materials is still a challenge for realizing high-efficient and stable p-i-n planar perovskite solar cells (pero-SCs). Here, we synthesized two π-conjugated small-molecule HTL materials through tailoring the backbone and conjugated side chain to carefully control molecular conformation. The resultant BDT-TPA- s Th containing a planar fused benzo[1,2- b :4,5- b ′]dithiophene (BDT) core and a conjugated thiophene side chain showed the planar conformation. X-ray crystallography showed a favorable stacking model in solid states under the parallel-displaced π-π and additional S-π weak-bond supramolecular interactions, thus achieving an obviously increased hole mobility without dopants. As an HTL material in p-i-n planar pero-SCs, the marginal solubility of BDT-TPA-sTh enabled inverse diffusion into the perovskite precursor solution for assisting the subsequent perovskite film growth and passivating the uncoordinated Pb 2+ ion defects. As a result, the planar p-i-n pero-SCs exhibited a champion power conversion efficiency (PCE) of 20.5% and enhanced moisture stability. Importantly, the BDT-TPA- s Th HTL material also showed weak thickness-photovoltaic dependence, and the pero-SCs with blade-coated BDT-TPA- s Th as a HTL achieved a 15.30% PCE for the 1-cm 2 modularized device. This HTL material design strategy is expected to pave the way toward high-performance, dopant-free and printing large-area planar p-i-n pero-SCs.