Exploring a lead-free organic–inorganic semiconducting hybrid with above-room-temperature dielectric phase transition

Recently, organic–inorganic hybrid lead halide perovskites have attracted great attention for optoelectronic applications, such as light-emitting diodes, photovoltaics and optoelectronics. Meanwhile, the flexible organic components of these compounds give rise to a large variety of important functions, such as dielectric phase transitions. However, those containing Pb are harmful to the environment in vast quantities. Herein, a lead-free organic–inorganic hybrid, (C(6)H(14)N)(2)BiCl(5) (CHA; C(6)H(14)N(+) is cyclohexylaminium), has been successfully developed. As expected, CHA exhibits an above-room-temperature solid phase transition at 325 K (T(c)), which was confirmed by the differential scanning calorimetry measurement and variable temperature single crystal X-ray diffraction analyses. Further analyses indicate the phase transition is mainly governed by the order–disorder transformation of organic cyclohexylaminium cations. Interestingly, during the process of phase transition, the dielectric constant (ε′) of CHA shows an obvious step-like anomaly, which displays a low dielectric constant state below T(c) and a high dielectric constant state above T(c). Furthermore, variable temperature conductivity combined with theoretical calculations demonstrate the notable semiconducting feature of CHA. It is believed that our work will provide useful strategies for exploring lead-free organic–inorganic semiconducting hybrid materials with above room temperature dielectric phase transitions.