Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers | 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 Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers Matthaeus Siebenhofer, Andreas Nenning, Christoph Rameshan, Peter Blaha, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3345186/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 26 Feb, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Improving materials for energy conversion and storage devices is deeply connected with an optimization of the surfaces of these materials. Surface modification has therefore emerged as a very promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of surface properties, in particular of the surface dipole and the work function, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of a mixed conducting host material and vice versa . The emerging surface dipoles are caused by changes in the energy landscape, leading to redistribution of electronic charge density and/or a geometric reorientation of the surface. As a proof of concept that this strategy is widely applicable to tailor surface properties, we examined the effect of ultra-thin decoration layers on the oxygen exchange kinetics of pristine thin films of structurally and chemically different mixed conducting oxides in very clean conditions by means of in-situ impedance spectroscopy during pulsed laser deposition ( i -PLD). The extended study confirms that basic decorations with a reduced surface work function lead to a substantial acceleration of the oxygen exchange on a material's surface. Computational results suggest that the underlying mechanism of the kinetic improvement relies on a modification of the energetics of charged O 2 adsorbates and substantiate their importance for the oxygen exchange reaction. Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry Physical sciences/Materials science/Condensed-matter physics/Surfaces, interfaces and thin films Physical sciences/Chemistry/Surface chemistry Physical sciences/Materials science/Materials for energy and catalysis/Electrochemistry/Fuel cells surface engineering work function surface dipole mixed conducting oxides surface modification Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SI.pdf Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 26 Feb, 2024 Read the published version in Nature Communications → Version 1 posted 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-3345186","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":234701378,"identity":"f1a69c06-1292-4561-a840-6a3b51070c3f","order_by":0,"name":"Matthaeus 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Surface modification has therefore emerged as a very promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of surface properties, in particular of the surface dipole and the work function, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of a mixed conducting host material and \u003ci\u003evice versa\u003c/i\u003e. The emerging surface dipoles are caused by changes in the energy landscape, leading to redistribution of electronic charge density and/or a geometric reorientation of the surface. As a proof of concept that this strategy is widely applicable to tailor surface properties, we examined the effect of ultra-thin decoration layers on the oxygen exchange kinetics of pristine thin films of structurally and chemically different mixed conducting oxides in very clean conditions by means of \u003ci\u003ein-situ\u003c/i\u003e impedance spectroscopy during pulsed laser deposition (\u003ci\u003ei\u003c/i\u003e-PLD). The extended study confirms that basic decorations with a reduced surface work function lead to a substantial acceleration of the oxygen exchange on a material's surface. 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