Formamidinium Perovskitizers and Aromatic Spacers Synergistically Building Bilayer Dion–Jacobson Perovskite Photoelectric Bulk Crystals

Two-dimensional (2D) multilayer Dion-Jacobson (DJ) phase organic inorganic hybrid perovskites (OIHPs) have attracted extensive research attention due to the high stability and excellent charge-transport properties in the optoelectronic field. However, the synthesis of 2D multilayer DJ OIHPs is still very challenging. Until now, only few multilayer DJ perovskites have been reported and most of them are based on volatile methylamine (MA) cations. Compared with MA-based OIHPs, the OIHPs constructed with formamidinium (FA) as perovskitizers not only improve the stability but also extend the light absorption range. Meanwhile, the introducing aromatic diamines as spacers could promote the electron-hole separation in such DJ hybrids. However, the DJ OIHP bulk single crystal constructed by using the advantages of FA as perovskitizers and aromatic diamines as spacers is still blank. Herein, we integrate the properties of organic cations and inorganic skeletons at a molecular-scale to construct a broadband-responsive 2D bilayer DJ perovskite (3AMPY)(FA)Pb₂I₇ [3AMPY = 3-(aminomethyl)pyridinium], which shows a fascinating detectivity from X-ray (5.23 × 10⁴ μC Gy_air^-1 cm^-2 at 200 V bias) and visible light (6 × 10¹² jones at 637 nm) to the near-infrared region (2.6 × 10⁹ jones at 780 nm). After an in-depth analysis of structure and optical properties, we found that the distortion degree of Pb-I-Pb bond angles between adjacent PbI₆ octahedra plays a crucial role on optical properties; on the other hand, the interlayer spacer cations (3AMPY) and intralayer perovskitizers (FA) mutual participate in the contribution of the conduction band, making (3AMPY)(FA)Pb₂I₇ have a narrow optical band gap of 1.54 eV. Such a 2D perovskite material with a wide spectra response will be the preferred choice for photodetection under complex conditions.