Defect dipole induced improved electrocaloric effect in modified NBT-6BT lead-free ceramics

Abstract

The Rietveld refinement of the polycrystalline powders of 1% Fe and Mn-doped (Na0.5Bi0.5)0.94Ba0.06Ti0.98V0.02O3 at the Ti-site confirmed a single rhombohedral (R3c) phase. The bandgap, (Eg) was affected by the anti-phase octahedral tilt angle and the spin-orbit splitting energy of Ti4+2p3/2 and Ti4+2p1/2 states. The decrease in Bi loss and increase in the binding energy of Ba due to Fe/Mn doping has been correlated to the strengthening of Bi-O and Ba-O bonds which was revealed from the XPS studies thereby further related to the average A-O bond length from structural studies. Hence, a reduction of oxygen vacancy (VO) for the doped samples has been justified. A significant improvement of the dielectric constant, relaxation time (τ0), and the decrease in conductivity due to doping was revealed from the frequency-dependent (10 Hz-1 MHz) dielectric measurement study. The conduction and relaxation process are dominated by the short-range movement of defects. The activation energy (Ea ~1 eV) revealed that there is a presence of double-ionized VOs. The ECE study showed a significant enhancement of the changes in entropy, ΔS, and the adiabatic temperature difference, ΔT, due to doping, with ΔT being highest in the Fe-doped sample. Such improvement of dielectric and ECE properties was confirmed due to the reduction of the mobility of oxygen vacancy because of the formation(MnTi′′−Vo••)/(MnTi′−Vo••)• and FeTi′′−Vo••/(FeTi′−Vo••)• defect dipoles. © 2022 Elsevier B.V.