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Hole-transport materials (HTMs) play an important role as hole scavenger materials in the most efficient perovskite solar cells (PSCs). Here, for the first time, two Ag-based metal organic complexes (HA1 and HA2) are employed as a new class of dopant-free hole-transport material for application in PSCs. These HTMs show excellent conductivity and hole-transport mobility. Consequently, the devices based on these two HTMs exhibit unusually high fill factors of 0.76 for HA1 and 0.78 for HA2, which are significantly higher than that obtained using spiro-OMeTAD (0.69). The cell based on HA1-HTM in its pristine form achieved a high power conversion efficiency of 11.98% under air conditions, which is comparable to the PCE of the cell employing the well-known doped spiro-MeOTAD (12.27%) under the same conditions. More importantly, their facile synthesis and purification without using column chromatography …