Light‐Promoted Electrostatic Adsorption of High‐Density Lewis Base Monolayers as Passivating Electron‐Selective Contacts

Achieving efficient passivating carrier‐selective contacts (PCSCs) plays a critical role in high‐performance photovoltaic devices. However, it is still challenging to achieve both an efficient carrier selectivity and high‐level passivation in a sole interlayer due to the thickness dependence of contact resistivity and passivation quality. Herein, a light‐promoted adsorption method is demonstrated to establish high‐density Lewis base polyethylenimine (PEI) monolayers as promising PCSCs. The promoted adsorption is attributed to the enhanced electrostatic interaction between PEI and semiconductor induced by the photo‐generated carriers. The derived angstrom‐scale PEI monolayer is demonstrated to simultaneously provide a low‐resistance electrical contact for electrons, a high‐level field‐effect passivation to semiconductor surface and an enhanced interfacial dipole formation at contact interface. By implementing this light‐promoted adsorbed PEI as a single‐layered PCSC for n‐type silicon solar cell, an efficiency of 19.5% with an open‐circuit voltage of 0.641 V and a high fill factor of 80.7% is achieved, which is one of the best results for devices with solution‐processed electron‐selective contacts. This work not only demonstrates a generic method to develop efficient PCSCs for solar cells but also provides a convenient strategy for the deposition of highly uniform, dense, and ultra‐thin coatings for diverse applications.