Polarization switching in ferroelectric capacitors is typically realized by application of an electrical bias to the capacitor electrodes and occurs via a complex process of domain structure reorganization. As the domain evolution in real devices is governed by the distribution of the nucleation centers, obtaining a domain structure of a desired configuration by electrical pulsing is challenging, if not impossible. Recent discovery of polarization reversal via the flexoelectric effect has opened a possibility for deterministic control of polarization in ferroelectric capacitors. In this paper, we demonstrate mechanical writing of arbitrary-shaped nanoscale domains in thin-film ferroelectric capacitors with graphene electrodes facilitated by a strain gradient induced by a tip of an atomic force microscope (AFM). A phase-field modeling prediction of a strong effect of graphene thickness on the threshold load required to initiate mechanical switching has been confirmed experimentally. Deliberate voltage-free domain writing represents a viable approach for development of functional devices based on domain topology and electronic properties of the domains and domain walls.

Ferroelectric domain walls are a rich source of emergent electronic properties and unusual polar order. Recent studies show that the configuration of ferroelectric walls can go well beyond the conventional Ising-type structure. Néel-, Bloch-, and vortex-like polar patterns have been observed, displaying strong similarities with the spin textures at magnetic domain walls. Here, the discovery of antiferroelectric domain walls in the uniaxial ferroelectric Pb₅Ge₃O₁₁ is reported. Highly mobile domain walls with an alternating displacement of Pb atoms are resolved, resulting in a cyclic 180° flip of dipole direction within the wall. Density functional theory calculations show that Pb₅Ge₃O₁₁ is hyperferroelectric, allowing the system to overcome the depolarization fields that usually suppress the antiparallel ordering of dipoles along the longitudinal direction. Interestingly, the antiferroelectric walls observed under the electron beam are energetically more costly than basic head-to-head or tail-to-tail walls. The results suggest a new type of excited domain-wall state, expanding previous studies on ferroelectric domain walls into the realm of antiferroic phenomena.

Adv. Mater. 2021, 33, 2006089 DOI: 10.1002/adma.202006089 Aviram Bhalla-Levine is hereby added as an author of the article. Avi was an undergraduate student who did some of the piezoresponse force microscopy (PFM) experiments in the work. He left the group in the summer of 2019. When preparing the figures for the submission, the authors overlooked the fact that Avi had acquired that data. To give proper credit, they are added as an author of the paper as given above in the correction author list. The author name is associated with affiliation 1: Z. Zhang, A. Bhalla-Levine, Dr. L. Xie, Dr. M. Kumari, Dr. S. Das, Z. Leng, Prof. L. W. Martin, Prof. R. Ramesh Department of Materials Science and Engineering University of California Berkeley, CA 94720, USA E-mail: rramesh@berkeley.edu.

The control of the in-plane domain evolution in ferroelectric thin films is not only critical to understanding ferroelectric phenomena but also to enabling functional device fabrication. However, in-plane polarized ferroelectric thin films typically exhibit complicated multi-domain states, not desirable for optoelectronic device performance. Here we report a strategy combining interfacial symmetry engineering and anisotropic strain to design single-domain, in-plane polarized ferroelectric BaTiO₃ thin films. Theoretical calculations predict the key role of the BaTiO₃/PrScO₃ [Formula: see text] substrate interfacial environment, where anisotropic strain, monoclinic distortions, and interfacial electrostatic potential stabilize a single-variant spontaneous polarization. A combination of scanning transmission electron microscopy, piezoresponse force microscopy, ferroelectric hysteresis loop measurements, and second harmonic generation measurements directly reveals the stabilization of the in-plane quasi-single-domain polarization state. This work offers design principles for engineering in-plane domains of ferroelectric oxide thin films, which is a prerequisite for high performance optoelectronic devices.

The synthesis of fully epitaxial ferroelectric Hf_0.5 Zr_0.5 O₂ (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb₂ Ir₂ O₇ (PIO) and Bi₂ Ru₂ O₇ (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.

Ferroelectric hafnium and zirconium oxides have undergone rapid scientific development over the last decade, pushing them to the forefront of ultralow-power electronic systems. Maximizing the potential application in memory devices or supercapacitors of these materials requires a combined effort by the scientific community to address technical limitations, which still hinder their application. Besides their favorable intrinsic material properties, HfO2-ZrO2 materials face challenges regarding their endurance, retention, wake-up effect, and high switching voltages. In this Roadmap, we intend to combine the expertise of chemistry, physics, material, and device engineers from leading experts in the ferroelectrics research community to set the direction of travel for these binary ferroelectric oxides. Here, we present a comprehensive overview of the current state of the art and offer readers an informed perspective of where this field is heading, what challenges need to be addressed, and possible applications and prospects for further development.