Switchable Photovoltaic Effect and Robust Nonlinear Optical Response in a High-Temperature Molecular Ferroelectric [C₈N₂H₂₂][PbI₄]

Hybrid organic–inorganic molecular ferroelectrics (HOIMFs) have garnered significant attention for their potential applications in nonvolatile memory and spintronic devices. However, few efforts have been devoted to the photoelectric properties of lead halide molecular ferroelectrics, despite the fact that robust ferroelectricity and flexibility are desirable for thin-film photoelectric devices. Herein, we present a novel lead halide molecular ferroelectric [C₈N₂H₂₂][PbI₄] (<b>1</b>) synthesized hydrothermally. A polar monoclinic structure of <b>1</b> was solved by single-crystal X-ray diffraction and second-harmonic generation (SHG) tests. A direct band gap of 2.36 eV was confirmed by UV–vis spectrum and theoretical calculation. Hysteresis measurements demonstrated inherent room-temperature (RT) ferroelectricity in <b>1</b> with a spontaneous polarization (<i>P</i>_s) of 3.2 μC/cm². The <b>1</b>-based photoelectric device shows a notable photovoltaic (PV) effect with <i>V</i>_oc ∼ 0.27 V, <i>J</i>_sc ∼ 38 nA/cm² under AM 1.5 G illumination, and a rapid response time of ∼1.5 ms. A considerable enhancement in PV performance has been achieved by adjusting the ferroelectric polarization, resulting in a maximum <i>V</i>_<i>oc</i> ∼ 0.75 V, <i>J</i>_sc ∼ 2.28 μA/cm². Notably, <b>1</b> exhibits a rather large SHG signal, which is approximately 2.61-fold higher than that of KH₂PO₄ (KDP) upon a 1064 nm laser radiation. This study offers a bright avenue for lead halide molecular ferroelectrics as promising optoelectronic devices and SHG materials.