Role of Ca doping on oxygen vacancy production in modulating dielectric, ferroelectric and magnetic polarization in BaTiO3 thin films

Chemical bath deposition, being an application oriented electroless technique, is used for the deposition of calcium doped barium titanate (Ba1-xCaxTiO3) thin films using glass substrate. Ca concentration is varied as x = 0.0, 0.02, 0.04, 0.06, 0.08, 0.10 and 0.12. As-deposited thin films show amorphous behavior, whereas, annealed thin films show crystalline nature. X-ray diffraction (XRD) analysis of annealed thin films shows a pure tetragonal phase of Perovskite barium calcium titanate thin films up to x = 0.08 dopant concentration, while XRD peak corresponding to CaO is observed at x = 0.10 and 0.12. Maximum optical transmission of 65% is observed under undoped and as-deposited conditions. Annealed thin films show 83% transmission under undoped condition. While decrease in transmission is observed with the increase of dopant concentration due to the presence of sub bands. High value of dielectric constant (i.e. ∼3800 at log f = 1.3) and low value of tangent loss (i.e.∼0.15 at log f = 1.3) is observed for x = 0.08 dopant concentration. Cole–Cole plots reveal the presence of two electrically active grains and grain boundary regions. Maximum value of spontaneous polarization Pmax (18.46 μC/cm2) is observed for x = 0.08 dopant concentration. Mixed para-ferromagnetic response is observed under undoped condition. S-shaped magnetic response is observed for x = 0.02–0.04 whereas, ferromagnetic curves are observed for x = 0.06–0.12. It is important to mention here that tetragonal Perovskite calcium doped barium titanate thin films with U-shaped dielectric constant and good ferroelectric properties are hard to find in literature.