π‐Expanded Carbazoles as Hole‐Selective Self‐Assembled Monolayers for High‐Performance Perovskite Solar Cells

Abstract Carbazole‐derived self‐assembled monolayers (SAMs) are promising hole‐selective materials for inverted perovskite solar cells (PSCs). However, they often possess small dipoles which prohibit them from effectively modulating the workfunction of ITO substrate, limiting the PSC photovoltage. Moreover, their properties can be drastically affected by even subtle structural modifications, undermining the final PSC performance. Here, we designed two carbazole‐derived SAMs, CbzPh and CbzNaph through asymmetric or helical π‐expansion for improved molecular dipole moment and strengthened π‐π interaction. The helical π‐expanded CbzNaph has the largest dipole, forming densely packed and ordered monolayer, facilitated by the highly ordered assembly observed in its π‐scaffold's single crystal. These synergistically modulate the perovskite crystallization atop and tune the ITO workfunction. Consequently, the champion PSC employing CbzNaph showed an excellent 24.1 % efficiency and improved stability.