Novel electrical conductivity properties in Ca-doped BiFeO₃ nanoparticles

The charge defective structure in Bi_1−x Ca _x FeO₃ (CBFO, x = 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3) nanoparticles (NPs) ranging from 140 to 25 nm as well as their relations to band gap and leakage current behavior are investigated. It is demonstrated that Ca doping effectively narrows the band gap from ~2.16 to ~2.02 eV, due to the appearance and accumulation of oxygen vacancy. Subsequently, enhanced electrical conductivity was obtained in these CBFO NPs, which leads to the appearance of a distinct threshold switching behavior in Ca-doped BFO NPs with higher conductivity at room temperature. Possible mechanisms for Ca doping effects on the electric conduction were discussed upon the interplay of NPs’ size effect and mobile charged defects on the basis of reduced particle size and the increased density of oxygen vacancy analyzed through X-ray photoelectron spectrum.