Combined electrostatic and strain engineering of BiFeO$_3$ thin films at the morphotropic phase boundary

Abstract: Multiferroic BiFeO$_3$ (BFO) possesses a rich phase diagram that allows strain tuning of its properties in thin-film form. In particular, at large compressive strain, a supertetragonal (T) phase with giant polarization is stabilized over the more common rhombohedral (R) structure. To utilize the functionality of such metastable BFO phases in device applications, it is essential to understand the ferroelectric phase evolution upon insertion in nanoscale heterostructures. Here, we explore the emergence of ferroelectric phases close to the morphotropic phase boundary in compressively strained BFO during thin-film growth using in-situ optical second harmonic generation. We find that the epitaxial films form at the growth temperature in the ideal T phase without critical thickness for the polarization. Signatures of T-like and R-like monoclinically distorted phases only appear upon sample cooling. We furthermore demonstrate a robustness of single-domain polarization in the high-temperature T phase during the growth of capacitor-like metal|ferroelectric|metal heterostructures. Here, a reduction in tetragonality of the T phase, rather than domain formation, lowers the electrostatic energy. At this lower tetragonality, density-functional calculations and scanning transmission electron microscopy point to the stabilization of a new metastable R-like monoclinic structure upon cooling the heterostructure down to room temperature. Our results thus show that the combination of strain and electrostatic phase stabilization in BFO heterostructures yields a prominent platform for exploring ferroelectric phases and realizing ultrathin ferroelectric devices.