Dielectric relaxation in ferroelectric perovskites can result from different inherent chemical and charge disorders within their crystal structures. Despite several theories on dielectric relaxations, the relationship between the concentration of oxygen vacancy ($V_{\mathrm{O}}$) and dielectric relaxation has not been studied in perovskite oxide thin films. In this work, we report a systematic investigation on the influence of the $V_{\mathrm{O}}^{\prime }\mathrm{s}$ on the dielectric relaxation of ${\mathrm{Ba}}_{0.85}{\mathrm{Ca}}_{0.15}{\mathrm{Ti}}_{0.9}{\mathrm{Zr}}_{0.1}{\mathrm{O}}_3$ (BCZT) epitaxial thin films grown with ${\mathrm{La}}_{0.7}{\mathrm{Sr}}_{0.3}{\mathrm{MnO}}_3$ (LSMO) top and bottom electrodes on single-crystal ${\mathrm{SrTiO}}_3$ (100) substrates using pulsed laser deposition. The ambient oxygen pressures during film growth were systematically varied to control the concentration of $V_{\mathrm{O}}$ in the epitaxial BCZT thin films. Low ambient oxygen pressure was found to enhance the tetragonality of the BCZT films and a systematic decrease in the tetragonality was observed at high oxygen pressure conditions as evidenced from x-ray diffraction (XRD) studies. Temperature dependent XRD analyses indicated a low-temperature anomaly near $\sim 160\mathrm{K}$ in the BCZT/LSMO heterostructures. Low-temperature dielectric measurements revealed relaxor dielectric response with broad frequency dependence of the dielectric constant. It is proposed that the low-temperature dielectric relaxation is possibly caused by dipolar clusters that are formed by the aggregation of correlated $V_{\mathrm{O}}$-induced dipolar defects within the films deposited under different ambient oxygen pressures. High-resolution transmission electron microscopy suggested the presence of the nanometer-sized $V_{\mathrm{O}}$ clusters as represented by the structural defects of average diameters of $\sim 5\mathrm{nm}$ in the BCZT films grown at variable ambient oxygen pressure. Activation energies of the aforesaid dipolar clusters, obtained from the Vogel-Fulcher fitting of the dielectric dispersion, showed a gradual increase in magnitude, as well as decreasing freezing temperatures, with decreasing concentrations of $V_{\mathrm{O}}$ in the BCZT films. From the theoretical analysis of the experimental data, it is postulated that the presence of the $V_{\mathrm{O}}$-induced dipolar defects affects the low-temperature dielectric relaxation in the BCZT thin films. This work significantly extends the understanding of $V_{\mathrm{O}}$-mediated dielectric relaxor behavior in complex perovskite oxide films.

• Received 24 December 2020
• Accepted 4 June 2021

DOI:https://doi.org/10.1103/PhysRevMaterials.5.064415