Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film

CaTiO₃ is a well-known incipient ferroelectric material that does not undergo a ferroelectric phase transition in spite of the intriguing dielectric constant behavior. Especially, unlike a prototypical incipient ferroelectric SrTiO₃, the paraelectric state of CaTiO₃ cannot be easily destroyed by small perturbations, including cation doping and epitaxial strain. We present that a nearly strain-free epitaxial CaTiO₃ film grown at a low oxygen partial pressure exhibits polarization–voltage hysteresis loops and the distinct difference of piezoresponse force microscopy phase signals, implying that a ferroelectric phase is induced. Such results are shown even at room temperature. We suggest that the observed ferroelectric behavior in CaTiO₃ film comes from the defect dipoles composed of vacancies inside the film. Using electron-probe microanalysis and optical absorption spectra measurements, we found that CaTiO₃ film has considerable Ca and O vacancies, forming the localized defect state in electronic structure. This work highlights the importance of vacancies and their clusters, such as defect dipoles, in understanding the electronic properties of perovskite oxide thin films, including ferroelectricity.