The Role of Fluorine-Substituted Positions on the Phase Transition in Organic–Inorganic Hybrid Perovskite Compounds

Abstract

Although research on organic–inorganic hybrid perovskites (OIHPs) has grown exponentially in the past two decades, the high phase transition temperature of OIHP materials is still one of the insurmountable difficulties. Herein, a series of A₂BX₄ type OIHP materials [(2,n-DFBA)₂PbCl₄] (n = 3, for 1; n = 4, for 2; n = 5, for 3; n = 6, for 4) have been prepared by reactions of double-substituted difluorobenzylamine (difluorobenzylamine = DFBA) with lead chloride in concentrated HCl aqueous solution. It was found the OIHP compounds 1–3 proceed a switchable phase transition with phase transition temperatures (T_c) at 449 K (1), 462 K (2) and 500 K (3), higher than that of the parent compound [(BA)₂PbCl₄] (BA = benzylammonium) at 438 K, but compound 4 exhibits no phase transition. A crystal structure analysis elucidated that the organic template ligands DFBA lead in the inorganic part in compounds 1–3 to a two-dimensional (2D) perovskite structure, while that in compound 4 leads to a one-dimensional (1D) chain structure. The different double-substituted positions of fluorine atoms on benzylamine have important influences on the phase transition in compounds 1–4.