2D Perovskites with Giant Excitonic Optical Nonlinearities for High‐Performance Sub‐Bandgap Photodetection

Two‐dimensional (2D) perovskites have proved to be promising semiconductors for photovoltaics, photonics, and optoelectronics. Here, a strategy is presented toward the realization of highly efficient, sub‐bandgap photodetection by employing excitonic effects in 2D Ruddlesden–Popper‐type halide perovskites (RPPs). On near resonance with 2D excitons, layered RPPs exhibit degenerate two‐photon absorption (D‐2PA) coefficients as giant as 0.2–0.64 cm MW^?1. 2D RPP‐based sub‐bandgap photodetectors show excellent detection performance in the near‐infrared (NIR): a two‐photon‐generated current responsivity up to 1.2 × 10⁴ cm² W^?2 s^?1, two orders of magnitude greater than InAsSbP‐pin photodiodes; and a dark current as low as 2 pA at room temperature. More intriguingly, layered‐RPP detectors are highly sensitive to the light polarization of incoming photons, showing a considerable anisotropy in their D‐2PA coefficients (β_001]/β_011] = 2.4, 70% larger than the ratios reported for zinc‐blende semiconductors). By controlling the thickness of the inorganic quantum well, it is found that layered RPPs of (C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇ can be utilized for three‐photon photodetection in the NIR region.