Achieving an ultra-high capacitive energy density in ferroelectric films consisting of superfine columnar nanograins

Well-crystallized perovskite ferroelectric films usually display a bulk-like polarization response (P) under an external electric field (E), i.e., a large P-E hysteresis loop featuring a sizable remnant polarization and an early polarization saturation. Such characteristics are undesirable for capacitive energy storage applications. In this work, we demonstrate an optimal P-E behavior, i.e., a small remnant polarization and a delayed polarization saturation, in perovskite BaTiO₃ films consisting of superfine columnar nanograins. In a low-temperature, nucleation-dominated sputtering deposition, an in-situ grown conductive buffer layer promotes the formation of these nanograins, which display a controllable diameter down to ~10 nm and extend throughout the film thickness. The deterioration of the remnant polarization and its delayed saturation under an electric field, can be attributed to a strong polarization-constraining effect from the densely-packed, non-ferroelectric grain boundaries, which is supported by a phase field modeling simulation. The resulted BaTiO₃ film capacitors integrated on Si at 350°C display a high recyclable energy density (W_rec~135±10 J/cm³) and efficiency (η~80%±4%) which are thickness-scalable. An intrinsically high power density, a simple and stable chemical composition, and good thermal (-150°C ~ 170°C) and cycling stabilities (up to ~ 2 × 10⁸ charge-discharge cycles) warrant a broad range of applications for these film capacitors.