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Advanced doped‐silicon‐layer‐based passivating contacts have boosted the power conversion efficiency (PCE) of single‐junction crystalline silicon (c‐Si) solar cells to over 26%. However, the inevitable parasitic light absorption of the doped silicon layers impedes further PCE improvement. To this end, alternative passivating contacts based on wide‐bandgap metal compounds (so‐called dopant‐free passivating contacts (DFPCs)) have attracted great attention, thanks to their potential merits in terms of parasitic absorption loss, ease‐of‐deposition, and cost. Intensive research activity has surrounded this topic with significant progress made in recent years. Various electron‐selective and hole‐selective contacts based on metal compounds have been successfully developed, and a champion PCE of 23.5% has been achieved for a c‐Si solar cell with a MoO_x‐based hole‐selective contact. In this work, the …