摘要： Environmental instability of Spiro-OMeTAD-based hole transport layer (HTL) caused due to rapid aggregation and hydration of its additive, Lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI), gives rise to an accelerated degradation of the resulting perovskite solar cells (PSCs). Herein, we show that replacing the Li-TFSI with the more hydrophobic alkaline-earth bis(trifluoromethanesulfonyl)imide additives, namely Mg-TFSI2 and Ca-TFSI2, can effectively stabilize the coordination complexes between the TFSI-salts and 4-tert-Butylpyridine, which in turn results in retarded additive aggregation and hydration, enabling enhanced moisture-resistance of the subsequent HTLs. Moreover, by manipulating this substitution method, we achieved high-quality HTLs with increased hole mobility, better-formed interface with the adjacent perovskite, allowing improved hole extraction process. Incorporating these HTLs into photovoltaic devices, we obtained a substantial performance improvement, with the champion PSC yielded a power conversion efficiency of over 20%. In addition, un-encapsulated devices stabilized by the alkaline-earth bis(trifluoromethanesulfonyl)imide additive maintained 83% its initial efficiency for 193 days after aging in ambient air (RH% = 55-70%).