Room-Temperature Photoferroelectrics Semiconductor Driven by the Interlayer Confinement Effect
Yueyue He, Zhuo Chen, Da‐Wei Fu, Zuoming Hou, Xian‐Ming Zhang, Dongying Fu
Abstract
With the assistance of the ferroelectrochemistry theory, many multifunctional organic–inorganic hybrid perovskites (OIHPs) ferroelectrics have been designed and studied. However, research on regulating ferroelectrics through the interlayer confinement effect in two-dimensional (2D) OIHPs is still rare. Herein, we regulated the strength of interlayer confinement by changing the length of the alkyl chain on organic cations, and precisely constructed a lead bromide ferroelectric (IPA) 2 PbBr 4 (IPA + is isopropylammonium) with a high Curie temperature ( T c ) of 340.5 K and a spontaneous polarization ( P s ) of 3.16 μC/cm 2 through a strong interlayer confinement effect. Compared with (IPA) 2 PbBr 4 ( T p = 370.5 K), (IBA) 2 PbBr 4 (IBA + is isobutylammonium, T p = 315 K) and (IAA) 2 PbBr 4 (IAA + is isoamylammonium, T p = 271 K) crystallized in the centrosymmetric space group P 2 1 / c, Cmca at room temperature (RT), respectively, while also having a lower phase transition temperature ( T p ). More importantly, the gradual decrease in interlayer spacing from 10.47 Å in (IAA) 2 PbBr 4, 7.73 Å in (IBA) 2 PbBr 4 to 5.79 Å in (IPA) 2 PbBr 4 enhances the interlayer confinement effect, leading to IBA + and IAA + cations in a disordered state at RT, while the IPA + cation can be arranged in an orderly and directional manner. Due to the differences in cations configuration, the impacts on the degree of distortion of inorganic skeleton and PbBr 6 octahedra are also different, ultimately reflected in the crystal structure. In short, the directional arrangement and order–disorder phase transition of IPA + cations induce the ferroelectricity of (IPA) 2 PbBr 4 through the strong confinement effect of the inorganic skeleton. Additionally, a single crystal device based on (IPA) 2 PbBr 4 was assembled, which exhibits a lower X-ray detection limit of 102 nGy/s in the self-driven mode. This work provides an effective strategy for designing high-temperature photoferroelectrics semiconductors.