Sang Wan Cho

Two-dimensional (2D) Ruddlesden–Popper (RP) perovskites hold great potential for novel optoelectronic applications. However, their unconventional optoelectronic properties are often compromised by a vulnerability to light irradiation, which leads to the formation of metallic Pb (Pb0) defects. This study investigates the passivation mechanism of these Pb0 defects in phenylethylammonium lead iodide (PEA2PbI4) using a strong molecular acceptor, 2,2′-(perfluoronaphthalene-2, 6-diylidene) dimalononitrile (F6-TCNNQ). In situ x-ray photoelectron spectroscopy results demonstrate that F6-TCNNQ effectively removes the light-induced Pb0 states, leading to the recovery of photoluminescence intensity in photodegraded PEA2PbI4 samples and significantly improving the photostability of pristine PEA2PbI4. F6-TCNNQ protects the terrace edge of PEA2PbI4, which is the site of initial degradation, as evidenced by atomic force microscopy and scanning electron microscopy analyses. In situ ultraviolet photoelectron spectroscopy measurements confirm substantial electron transfer from Pb0 to F6-TCNNQ, causing the oxidation of Pb0 to Pb2+. Furthermore, the staggered energy level alignment prevents electron transfer from the valence band maximum of PEA2PbI4 to the lowest unoccupied molecular orbital of F6-TCNNQ, thereby preserving the pristine electronic structure of PEA2PbI4. These findings provide new insights into defect passivation in 2D RP perovskites and offer a design strategy for highly stable optoelectronic devices.