New insights into structural, optical, electrical and thermoelectric behavior of Na_0.5Bi_0.5TiO₃ single crystals

The single crystals of lead-free Na_0.5Bi_0.5TiO₃ were grown using the Czochralski method. The energy gaps determined from X-ray photoelectron spectroscopy (XPS) and optical measurements were approximately 2.92 eV. The current-voltage characteristics, depolarization current, dc (σ_dc) and ac (σ_ac) electrical conductivity, and Seebeck coefficient of the crystals were investigated. The frequency/temperature-dependent electrical properties were also measured and analyzed through complex impedance spectroscopy. An overlapping reversible insulator-metal transition (resistive switching) on nanoscales, caused by the electric field, was detected. Most of these properties were measured for the first time. The activation energy values determined from the conductivity data, the imaginary part of the electric impedance and the modulus indicate that the relaxation process in the high-temperature range is attributable to both single and double ionized oxygen vacancies, in combination with the hopping of electrons between Ti⁴⁺ and Ti³⁺. P-type electrical conductivity was also found. These discoveries create new possibilities of reducing the electrical conductivity of NBT and improving the process of effectively poling this material. Our results indicate the possibility of tuning the material properties by intentionally creating non-stoichiometry/structural defects (oxygen vacancies, cation excess and cation deficiency).