Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films

摘要

Ferroelectricity and piezoelectricity are desirable for a variety of high-temperature applications such as actuators and sensors in heat engines, high-temperature manufacturing, and space technologies; however, the material candidates are currently limited. Here, we demonstrate that CaTiOsub3/sub, the prototype perovskite mineral, abundantly found in the Earth, which as a nonpolar material in bulk form, becomes a high-temperature ferroelectric oxide under compressive strain when grown as a thin film. A strain-phase-temperature diagram of CaTiOsub3/sub films is created by growing films on various substrates with different in plane strains in order to map out the polar behavior for compressive and tensile strain. Using temperature dependent optical second harmonic generation analysis, we show that tensile strained films exhibit predominantly in-plane polarization with orthorhombiclike point group symmetry with a phase transition below room temperature. On the other hand, compressively strained CaTiOsub3/sub films exhibit a near-tetragonal unit cell with a c / a ratio of 1.03, larger than that of classic ferroelectric, e.g., BaTiOsub3/sub ( c / a ～ 1.01). These films exhibit a robust and switchable out-of-plane polarization at room temperature, with a ferroelectric transition temperature up to ～800 K. Density functional theory calculations reveal that compressive strain gives rise to a large out-of-plane displacement of Ti-cations inside the TiOsub6/sub octahedral cages and is the major contributor to the calculated polarization of ～9 μ C/cmsup2/sup. Given that nearly half of the perovskites exhibit the bulk symmetry of CaTiOsub3/sub, compressive strain tuning of this perovskite family may prove to be a fertile ground for the discovery of strain-induced piezoelectrics and ferroelectrics at high-temperatures.