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In this study, we achieved a facile and low-cost (18-22 USD/g) synthesis of spiro[fluorene-9,9-phenanthren-10-one]-based interfacial layer materials (MSs; designated MS-PC, MS-PA, MS-OC, and MS-OA). Carbazoles and dimethylacridine substituents with an extended π-conjugation achieved through ortho- or para-orientations were used as donors at the spiro[fluorene-9,9'-phenanthren-10'-one] moiety. Highly efficient and stable inverted perovskite solar cells (PSCs) with the device architecture of ITO/NiO x /MSs/perovskite/PC61BM/BCP/Ag can be ach