Giant and Broadband Multiphoton Absorption Nonlinearities of a 2D Organometallic Perovskite Ferroelectric

Multiphoton absorption (MPA) has been utilized for important technological applications. High-order multiphoton harvesting (e.g., five-photon absorption, 5PA) exhibits unique properties that could benefit biophotonics. Within this field, perovskite oxide ferroelectrics (e.g., BaTiO3 ) enable low-order optical nonlinearities of 2PA/3PA processes. However, it is challenging to obtain efficient, high-order 5PA effects. Herein, for the first time, giant and broadband MPA properties are presented in the 2D hybrid perovskite ferroelectric (IA)2 (MA)2 Pb3 Br10 (1; IA = isoamylammonium and MA = methylammonium), where multiphoton-excited optical nonlinearities related to different MPA mechanisms over a broadband range of 550-2400 nm are observed. Strikingly, its 5PA absorption cross-section (σ5 ) reaches up to 1.2 × 10-132 cm10 s4 photon-4 (at 2400 nm), almost 10 orders larger than some state-of-the-art organic molecules and a record-high value among all known ferroelectrics. This unprecedented 5PA effect results from the quantum-confined motif of inorganic trilayer sheets (wells) and organic cations (barriers) in 1. Moreover, its large ferroelectric polarization of 5 µC cm-2 could promote modulation of MPA effects under external electric fields. As far as it is known, this is the first report on giant, broadband high-order MPA properties in ferroelectrics, which provides potential, novel electric-ordered materials for next-generation biophotonic applications.