2D Phase Purity Determines Charge-Transfer Yield at 3D/2D Lead Halide Perovskite Heterojunctions

Targeted functionalization of 3D perovskite with a 2D passivation layer via R-NH3I treatment has emerged as an effective strategy for enhancing both the efficiency and chemical stability of ABX(3) perovskite solar cells, but the underlying mechanisms behind these improvements remain unclear. Here, we assign a passivation mechanism where RNH3I reacts with excess PbI2 in the MAPbI(3) film and unsaturated PbI6 octahedra to form (R-NH3)(2)(MA)(n-1)PbnI3n+1. Crucially, we show that precise control of the 2D (RNH3)(2)(MA)(n-1)PbnI3n+1 layer underpins performance improvements: n = 1 yields over a 2-fold improvement in hole injection to the HTL; n > 1 deteriorates hole injection. Ultrafast transient absorption spectroscopy suggests this n-dependence is rooted in the fact that fast (<6 ns) hole injection does not occur between the 3D and 2D layers. These results help explain contemporary empirical findings in the field and set out an important design rule for the further optimization of multidimensional perovskite optoelectronics.