Exploring a Lead-free Semiconducting Hybrid Ferroelectric with a Zero-Dimensional Perovskite-like Structure

Perovskite lead halides (CH3NH3PbI3) have recently taken a promising position in photovoltaics and optoelectronics because of remarkable semiconducting properties and possible ferroelectricity. However, the potential toxicity of lead arouses great environmental concern for widespread application. A new chemically tailored lead-free semiconducting hybrid ferroelectric is reported, N-methylpyrrolidinium)(3)Sb2Br9 (1), which consists of a zero-dimensional (0-D) perovskite-like anionic framework connected by cornersharing SbBr6 coordinated octahedra. It presents a large ferroelectric spontaneous polarization of approximately 7.6 mu C cm(-2), as well as notable semiconducting properties, including positive temperature-dependent conductivity and ultraviolet-sensitive photoconductivity. Theoretical analysis of electronic structure and energy gap discloses a dominant contribution of the 0-D perovskite-like structure to the semiconducting properties of the material. This finding throws light on the rational design of new perovskite-like hybrids, especially lead-free semiconducting ferroelectrics.