Pressure-Induced Abnormal Electrical Transport Transition from Pure Electronic to Mixed Ionic–Electronic in Multiferroic BiFeO3 Ceramics

Abstract

Pressure-induced structural changes could induce changes in transport properties and lead to a better understanding of the structure–property relationship. The evolution of the carrier transport properties of BiFeO3 (BFO) ceramics under a high pressure was investigated through impedance spectroscopy measurements at room temperature combined with first-principles calculations. A pressure-induced abnormal transition from pure electronic to mixed ionic–electronic was found in the BFO ceramics Cmmm and Pnma phases at 7.67 and 11.01 GPa, respectively. The pressure-induced structural phase transition from the R3c phase to Cmmm and then to Pnma was responsible for the change in electrical transport behavior from pure electronic to mixed ionic–electronic conduction, accompanied by a decrease in ionic resistance. The calculations of electronic structures and electron localization function from 1 atm to 40 GPa indicated that the ionic conduction in the Pnma phase resulted from the weakened Coulomb screen of the localized electron background to O2– between Bi3+ and O2–. This work provides a critical insight into the understanding of the relationship between structure and conduction and facilitates the application of ferroelectric materials in photoelectric fields.