Incorporating Guanidinium as Perovskitizer‐Cation of Two‐Dimensional Metal Halide for Crystal‐Array Photodetectors

Two-dimensional (2D) hybrid perovskites are recently emerging as a potential family of semiconductors for versatile optoelectronic applications. Currently, the "perovskitizer" moieties are rigidly limited to small-size cations, while few 2D metal-halides containing guanidinium cations inside perovskite cages have been studied for photodetection. Herein, we present a new 2D hybrid perovskite, (i-BA)2 (G)Pb2 I7 (where G is guanidinium and i-BA is isobutylammonium), which adopts a bilayered framework of {GPb2 I7 }. Single-crystal structure analyses disclose that G cations act as the perovskitizer, confined in the flexible perovskite cages formed by the distorted PbI6 octahedra. Such inorganic sheets are crucial to the superior semiconducting properties and optical bandgap, as verified by the density functional theory calculation. Furthermore, its planar crystal-array photodetector shows fascinating photoelectric performance, including a quite low dark current (∼4.6×10-11 A), a large current switching ratio (∼1.0×103 ), and a notable photo-responsivity of ∼0.72 A W-1 , suggesting great potential of (i-BA)2 (G)Pb2 I7 for photodetection.