Deploying a Dipole Electric Field at the CsPbI₃ Perovskite/Carbon Interface for Enhancing Hole Extraction and Photovoltaic Performance

Carbon‐based CsPbI3 perovskite solar cells without hole transporter (C‐PSCs) have achieved intense attention due to its simple device structure and high chemical stability. However, the severe interface energy loss at the CsPbI3/carbon interface, attributed to the lower hole selectivity for inefficient charge separation, greatly limits device performance. Hence, dipole electric field (DEF) is deployed at the above interface to address the above issue by using a pole molecule, 4‐trifluoromethyl‐Phenylammonium iodide (CF3‐PAI), in which the ─NH3 group anchors on the perovskite surface and the ─CF3 group extends away from it and connects with carbon electrode. The DEF is proven to align with the built‐in electric field, that is pointing toward carbon electrode, which well enhances hole selectivity and charge separation at the interface. Besides, CF3‐PAI molecules also serve as defect passivator for reducing trap state density, which further suppresses defect‐induced non‐radiative recombination. Consequently, the CsPbI3 C‐PSCs achieve an excellent efficiency of 18.33% with a high VOC of 1.144 V for inorganic C‐PSCs without hole transporter.