| Summary: | Bismuth ferrite (BiFeO<sub>3</sub>, BFO) is still widely investigated both because of the great diversity of its possible applications and from the perspective of intrinsic defect engineering in the perovskite structure. Defect control in BiFeO<sub>3</sub> semiconductors could provide a key technology for overcoming undesirable limitations, namely, a strong leakage current, which is attributed to the presence of oxygen vacancies (<i>V<sub>O</sub></i>) and Bi vacancies (<i>V<sub>Bi</sub></i>). Our study proposes a hydrothermal method for the reduction of the concentration of <i>V<sub>Bi</sub></i> during the ceramic synthesis of BiFeO<sub>3</sub>.Using hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) as part of the medium, <i>p-type</i> BiFeO<sub>3</sub> ceramics characterized by their low conductivity were obtained. Hydrogen peroxide acted as the electron donor in the perovskite structure, controlling <i>V<sub>Bi</sub></i> in the BiFeO<sub>3</sub> semiconductor, which caused the dielectric constant and loss to decrease along with the electrical resistivity. The reduction of Bi vacancies highlighted by a FT-IR and Mott—Schottky analysis has an expected contribution to the dielectric characteristic. A decrease in the dielectric constant (with approximately 40%) and loss (3 times) and an increase of the electrical resistivity (by 3 times) was achieved by the hydrogen peroxide-assisted hydrothermal synthesized BFO ceramics, as compared with the hydrothermal synthesized BFOs.
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