Phonon-pair-driven Ferroelectricity Causes Costless Domain-walls and Bulk-boundary Duality

Abstract: Ferroelectric domain walls, recognized as distinct from the bulk in terms of symmetry, structure, and electronic properties, host exotic phenomena including conductive walls, ferroelectric vortices, novel topologies, and negative capacitance. Contrary to conventional understanding, our study reveals that the structure of domain walls in HfO2 closely resembles its bulk. First, our first-principles simulations unveil that the robust ferroelectricity is supported by bosonic pairing of all the anionic phonons in bulk HfO2. Strikingly, the paired phonons strongly bond with each other and successfully reach the center of the domain wall without losing their integrity and produce bulk-like domain walls. We then confirmed preservation of the bulk phonon displacements and consequently full revival of the bulk structure at domain walls via aberration-corrected STEM. The newly found duality between the bulk and the domain wall sheds light on previously enigmatic properties such as zero-energy domain walls, perfect Ising-type polar ordering, and exceptionally robust ferroelectricity at the sub-nm scales. The phonon-pairing discovered here is robust against physical boundaries such as domain walls and enables zero momentum and zero-energy cost local ferroelectric switching. This phenomenon demonstrated in Si-compatible ferroelectrics provides a novel technological platform where data storage on domain walls is as feasible as that within the domains, thereby expanding the potential for high-density data storage and advanced ferroelectric applications.