Atomic mechanism of polarization-controlled surface reconstruction in ferroelectric thin films

At the ferroelectric surface, the broken translational symmetry induced bound charge should significantly alter the local atomic configurations. Experimentally revealing the atomic structure of ferroelectric surface, however, is very challenging due to the strong spatial variety between nano-sized domains, and strong interactions between the polarization and other structural parameters. Here, we study surface structures of Pb(Zr0.2Ti0.8)O-3 thin film by using the annular bright-field imaging. We find that six atomic layers with suppressed polarization and a charged 180 degrees domain wall are at negatively poled surfaces, no reconstruction exists at positively poled surfaces, and seven atomic layers with suppressed polarization and a charged 90 degrees domain wall exist at nominally neutral surfaces in ferroelastic domains. Our results provide critical insights into engineering ferroelectric thin films, fine grain ceramics and surface chemistry devices. The state-of-the-art methodology demonstrated here can greatly advance our understanding of surface science for oxides.National Program for Thousand Young Talents of China; Program Peking-Tsinghua-IOP Collaborative Innovation Center of Quantum Matter; National Natural Science Foundation of China [51502007, 11327902]; Japan Society for the Promotion of Science fellowship; Ministry of Science and Technology, China [MOST 103-2119-M-009-003-MY3]; Center for Interdisciplinary Science of National Chiao Tung University; Japan Society for the Promotion of Science [25106003]; MEXT, Japan [12024046]SCI(E)ARTICLEp-gao@pku.edu.cn; ikuhara@sigma.t.u-tokyo.ac.jp