Universal insights into the origin of ferroelectricity in doped hafnia

Universal insights into the origin of ferroelectricity in doped hafnia | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Universal insights into the origin of ferroelectricity in doped hafnia Minghua Tang, Gang Li, Shaoan Yan, Yulin Liu, Wanli Zhang, Yongguang Xiao, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4207666/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 15 Feb, 2025 Read the published version in npj Computational Materials → Version 1 posted 9 You are reading this latest preprint version Abstract Although doping stands out as a crucial method for inducing ferroelectricity in hafnia films, the mechanisms behind it remains controversial. Notably, the carriers introduced by heterovalent dopants have been largely overlooked. Here, through first-principles studies, we elucidate the key role played by the rich phase transition mechanism under carrier doping in understanding the origin of hafnia ferroelectricity. Electron doping orchestrates a metastable polar phase to stable antipolar phase transformation, driven by strong screening effects and the decay of nonpolar covalent bonds, resulting in the rarity of n-type dopants. Conversely, a delicate balanced interplay of weak screening effects and strengthened polar covalent bonds drives hole maintains robust ferroelectricity. However, the hole distribution pattern markedly affects the total energy difference across phases, culminating in a striking ground-state phase transition from nonpolar monoclinic phase to polar orthorhombic phase to nonpolar cube phase as the hole concentration increases. This phase transition is consistent with the variation trend of the highest phase fraction in hafnia films with the p-type dopants concentration. In addition, the thickness of hafnia ferroelectric films is easily stabilized on the 1 nm, unlike perovskite ferroelectrics, due to the hole enhanced polar distortion. Our theoretical analyses seamlessly align with experimental measurements, offering innovative perspectives for the preparation of robust hafnia-based ferroelectricity films through doping or interface engineering. Physical sciences/Materials science/Condensed-matter physics/Ferroelectrics and multiferroics Physical sciences/Materials science/Condensed-matter physics/Surfaces, interfaces and thin films Full Text Additional Declarations (Not answered) Supplementary Files SI2024.4.2.docx Cite Share Download PDF Status: Published Journal Publication published 15 Feb, 2025 Read the published version in npj Computational Materials → Version 1 posted Editorial decision: revise 21 May, 2024 Review # 2 received at journal 14 May, 2024 Review # 1 received at journal 30 Apr, 2024 Reviewer # 2 agreed at journal 26 Apr, 2024 Reviewer # 1 agreed at journal 15 Apr, 2024 Reviewers invited by journal 15 Apr, 2024 Submission checks completed at journal 03 Apr, 2024 First submitted to journal 02 Apr, 2024 Editor assigned by journal 02 Apr, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4207666","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":291462605,"identity":"2ec733cb-0838-4006-baa5-ec55b5802a64","order_by":0,"name":"Minghua 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This phase transition is consistent with the variation trend of the highest phase fraction in hafnia films with the p-type dopants concentration. In addition, the thickness of hafnia ferroelectric films is easily stabilized on the 1 nm, unlike perovskite ferroelectrics, due to the hole enhanced polar distortion. 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