Ferroelectricity of the Orthorhombic and Tetragonal MAPbBr₃ Single Crystal

Hybrid organic-inorganic halide perovskites (HOIPs) MAPbBr₃ and their ramifications have emerged because of the photovoltaic, optical, and other fascinating performances of HOIPs in recent years. However, many intrinsic properties, such as crystal structure and ferroelectricity, are still controversial. In this work, the ferroelectricity of the orthorhombic and tetragonal MAPbBr₃ single crystal was confirmed through the dielectric behavior versus bias electric field ε( E), the temperature-dependent pyroelectric current with positive/negative poling, and the positive-up-negative-down (PUND) measurements. The electric field dependence of dielectric constant curves shows a butterfly type shape in the orthorhombic and tetragonal phase. The pyroelectric current shows two maxima at 155 and 245 K, corresponding to ferroelectric-ferroelectric and ferroelectric-paraelectric phase transitions, respectively. In particular, the direction of the pyroelectric current can be reversed by a positive or negative poling electric field, which is the assertive evidence of ferroelectricity. The PUND measurements act as the most convincing proof of the ferroelectricity of the MAPbBr₃ single crystal. This work reports new evidence of the ferroelectric properties of the MAPbBr₃ single crystal, which provides the intrinsic property when considering their high power conversion efficiencies.