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HfO2, a simple binary oxide, holds ultra-scalable ferroelectricity integrable into silicon technology. Polar orthorhombic (Pbc21) form in ultra-thin-films ascribes as the plausible root-cause of the astonishing ferroelectricity, which has thought not attainable in bulk crystals. Though, perplexities remain primarily due to the polymorphic nature and the characterization challenges at small-length scales. Herein, utilizing a state-of-the-art Laser-Diode-heated Floating Zone technique, we report ferroelectricity in bulk single-crystalline HfO2:Y as well as the presence of anti-polar Pbca phase at different Y concentrations. Neutron diffraction and atomic imaging demonstrate (anti-)polar crystallographic signatures and abundant 90o/180o ferroelectric domains in addition to the switchable polarization with little wake-up effects. Density-functional theory calculations suggest that the Yttrium doping and rapid cooling are the key factors for the desired phase. Our observations provide new insights into the polymorphic nature and phase controlling of HfO2, remove the upper size limit for ferroelectricity, and also pave a new road toward the next-generation ferroelectric devices.
Ferroelectric HfO2-based materials hold great potential for widespread integration of ferroelectricity into modern electronics due to their robust ferroelectric properties at the nanoscale and compatibility with the existing Si technology. Earlier wo
Wake-up effect is still an obstacle in the commercialization of hafnia-based ferroelectric thin films. In this work, we investigate the effect of defects, controlled by ozone dosage, on the field cycling behavior of the atomic layer deposited Hf0.5Zr
Ferroelectric HfO2 (fe-HfO2) has garnered increasing research interest for nonvolatile memories and low-power transistors. However, many challenges are to be resolved. One of them is the depolarizing effect that is commonly attributed to the formatio
A wake-up free Hf0.5Zr0.5O2 (HZO) ferroelectric film with the highest remnant polarization (Pr) value to-date was achieved through tuning of the ozone pulse duration, the annealing process, and the metal/insulator interface. The ozone dosage during t
Based on an accurate first principles description of the energetics in H-bonded KDP, we conduct a first study of nuclear quantum effects and of the changes brought about by deuteration. Cluster tunneling involving also heavy ions is allowed, the main