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The antisolvent-assisted spin-coating still lags behind the thermal evaporation method in fabricating perovskite films atop industrially textured silicon wafers in making monolithic perovskite/silicon solar cells (P/S-TSCs). The inhomogeneity of hole-selective self-assembled monolayers (SAMs) often arises from the insufficient bonding between hygroscopic phosphonic acid anchors and metal oxide. To address this, a mixed-SAM strategy (Mx-SAM) is proposed to enhance the adsorption energy of SAMs on the ITO surface, facilitate the formation of dense and humidity-resistant hole-selective layer (HSL) on substrates, and improve hole transport capabilities. With the aid of the Mx-SAM strategy, the optimized wide-bandgap PSCs achieved an impressive power conversion efficiency (PCE) of 22.63% with an exceptionally high fill factor (FF) of 86.67% using the 1.68 eV perovskite. Moreover, they exhibited enhanced stability under damp-heat conditions (ISOS-D-3, 85% RH, 85 degrees C) with a T90 of 900 h for encapsulated PSCs, representing one of the best performances for wide-bandgap PSCs. When further extending the Mx-SAM strategy to making P/S-TSCs using silicon wafers from industry, a remarkable efficiency of 28.07% is reached while upholding outstanding reproducibility. This strategy holds significant promise for the feasibility of fabricating industrially-compatible P/S-TSCs.|A mixed-SAM strategy (Mx-SAM) is proposed to enhance the adsorption energy of SAMs on the ITO surface, facilitate the formation of dense and humidity-resistant hole-selective layer (HSL) on substrates, the wide-bandgap (1.68 eV) PSCs achieved a PCE of 22.63%, and the fabricated industrially-compatible P/S-TSCs through antisolvent-assisted crystallization strategies achieve a remarkable efficiency of 28.07%. image
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