Defect engineering has been a powerful tool to enable the creation of exotic phases and the discovery of intriguing phenomena in ferroelectric oxides. However, accurate control the concentration of defects remains a big challenge. In this work, ion implantation, that can provide controllable point defects, allows us the ability to produce a controlled defect-driven true super-tetragonal (T) phase with enhanced tetragonality in ferroelectric BiFeO3 thin films. This point defect engineering is found to drive the phase transition from the as-grown mixed rhombohedral-like (R) and tetragonal-like (MC) phase to true tetragonal (T) symmetry. By further increasing the injected dose of He ion, we demonstrate an enhanced tetragonality super-tetragonal (super-T) phase with the largest c/a ratio (~ 1.3) that has ever been experimentally achieved in BiFeO3. A combination of morphology change and domain evolution further confirm that the mixed R/MC phase structure transforms to the single-domain-state true tetragonal phase. Moreover, the re-emergence of R phase and in-plane stripe nanodomains after heat treatment reveal the memory effect and reversible phase transition. Our findings demonstrate the control of R-Mc-T-super T symmetry changes and the creation of true T phase BiFeO3 with enhanced tetragonality through controllable defect engineering. This work also provides a pathway to generate large tetragonality (or c/a ratio) that could be extended to other ferroelectric material systems (such as PbTiO3, BaTiO3 and HfO2) which may lead to strong polarization enhancement.
تحميل البحث