Cavity-Selective Host–Guest Assembly for Modular Buried-Interface Engineering in Perovskite Solar Cells
Yunjia Wu, Sihao Huang, Yude Wei, Jiayan Wang, Qiuju Liu, Wenqi Ge, Zhiyang Yan, Yinping Zeng, Yang An, Chaocheng Zhou, Jie Bai, Weihai Sun, Hua BaiAbstract
Buried-interface engineering is critical for inverted perovskite solar cells, yet integrating anchoring, charge transport, electrostatic regulation, and defect passivation within single molecular systems often creates intrinsic trade-offs. Here, we use cavity-selective host–guest recognition to construct a modular, recognition-directed interface. The cavity of dipolar 4-tert-butylsulfonylcalix[4]arene (tBSCA) selectively accommodates the terminal phenyl group of substrate-anchored Ph-4PACz. Comparisons with a structurally related calixarene analogue and competing inclusion orientations identify a thermodynamically preferred Ph-4PACz-tBSCA configuration, distinguishing cavity-selective association from nonspecific interactions. This preferred configuration underpins a preferentially organized dipolar interface that retains Ph-4PACz-mediated anchoring and charge transport while enabling tBSCA to regulate interfacial electrostatics, reduce interfacial defect sites, and suppress defect-assisted halide migration and interfacial accumulation. The resulting devices achieve a PCE of 27.36% (certified at 26.74%), and a 110 cm2 module delivers a certified efficiency of 22.61%. These results demonstrate configuration-selective molecular recognition as a strategy for the modular organization of complementary functions at buried perovskite interfaces.