Visualizing band alignment across 2D/3D perovskite heterointerfaces of solar cells with light-modulated scanning tunneling microscopy

Abstract

Graded 2D perovskite capping shells with continuously upshifting valence bands, produced by tailored dimensional engineering, can effectively extract holes from 3D perovskite cores. Real-space observation of electronic structures will fully reveal the operating mechanisms of 2D/3D hybrid perovskite solar cells (PSCs). Here, for the first time, light-modulated scanning tunneling microscopy visualizes the cross-sectional band alignment across 2D (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) n-1 Pb n I 3n+1 /3D CH 3 NH 3 PbI 3 stacked perovskites. By systematically analyzing their electronic configuration, the mixed-dimensional perovskite band structure along the vertical 3D-to-2D direction can be spatially resolved. Remarkably, the electric field in the 2D perovskite is larger under light illumination than under dark conditions, resulting in an increase in the concentration of holes and electrons distributed in the 2D and 3D perovskites, respectively. Benefiting from this electronic reconstruction, charge recombination is suppressed, thereby significantly promoting the 2D/3D PSC performance. Moreover, our method opens an avenue for direct, local mapping of optoelectronic device energy levels. • Real spacing energy band distribution of photo-activated 2D/3D perovskites is first mapped. • Visualization of photocarrier dynamics is demonstrated, promote efficiencies of 2D/3D perovskite solar cells. • The electric field in the 2D perovskite is enhanced under light illumination. • This LM-XSTM technology will be used for other semiconductor devices.