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The integration of p\u2010type SAMs has driven the power conversion efficiency (PCE) of inverted p\u2010i\u2010n structured PVSCs to a world record efficiency of 26.7%. However, in PVSCs with traditional n\u2010i\u2010p structures, n\u2010type SAMs have not yet achieved comparable breakthroughs. Therefore, to unlock the full potential of n\u2010type SAMs, this review provides a comprehensive summary of their molecular structures, deposition methods, and passivation mechanisms. Recent advances in various n\u2010type SAMs, including fullerene\u2010based, naphthalene imide\u2010based, benzene\u2010based SAMs, and SAMs with other structures have been discussed in detail. 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