Multifunctional Pyroelectric and Electrocaloric response through Eu3+ doping in 0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3 ceramics at Morphotropic Phase Boundary

Multifunctional Pyroelectric and Electrocaloric response through Eu3+ doping in 0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3 ceramics at Morphotropic Phase Boundary | 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 Research Article Multifunctional Pyroelectric and Electrocaloric response through Eu3+ doping in 0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3 ceramics at Morphotropic Phase Boundary Shubham Modgil, Mukul Kumar, Arun Kumar Singh, Shobhna Dhiman, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8807205/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 08 Apr, 2026 Read the published version in Journal of Materials Science: Materials in Electronics → Version 1 posted You are reading this latest preprint version Abstract This study presents a strategy to enhance the pyroelectric and electrocaloric responses at room temperature by tailoring the Landau free-energy landscape of a ternary morphotropic phase boundary (MPB) composition 0.55Pb(Ni 1/3 Nb 2/3 )O 3 -0.135PbZrO 3 -0.315PbTiO 3 + xEu 2 O 3 (x = 0, 0.01 & 0.02). Eu 3+ substitution at the A-site reduces the effective ionic spacing, inducing octahedral tilting and stabilizing a lower-symmetry crystal structure, predominantly rhombohedral, in the vicinity of room temperature. The associated local lattice distortion and charge imbalance promote relaxor behaviour in the PNN-PZ-PT system. A pronounced enhancement in pyroelectric performance is observed for the x = 0.02 composition, with the pyroelectric coefficient reaching ~ 33.34 ×10 − 4 C/m 2 K and the corresponding pyroelectric figures of merits (FOMs) attain values of \(\:{F}_{i}\) ~ 1993 pm/V, \(\:{F}_{v}\) ~ 0.01592 m 2 /C, \(\:{F}_{d}\) ~23.57 µ(Pa) −0.5 , \(\:{F}_{e}\) ~107 Jm 3 /K and \(\:{F}_{e}^{*}\) ~26.48 pm 3 /N. Notably, electrocaloric measurements reveal the emergence of an orthorhombic phase near room temperature, resulting in an improved electrocaloric temperature change. Concurrently, Eu 3+ doping suppresses the inverse piezoelectric coefficient ( \(\:{d}_{33}^{*}\) ) from 1036 pm/V for x = 0 to 460 pm/V for x = 0.02 sample indicating reduced electromechanical coupling, while the energy storage density exhibits an improvement near the ferroelectric-paraelectric phase transition. These findings demonstrate that Eu 3+ modified PNN-PZ-PT ceramics offer a tunable multifunctional platform with potential applications in solid-state cooling, infrared detection, and thermal energy harvesting. PNN-PZ-PT Morphotropic phase boundary ferroelectric electrocaloric pyroelectric Full Text Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 08 Apr, 2026 Read the published version in Journal of Materials Science: Materials in Electronics → 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-8807205","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":592075323,"identity":"ae9b1305-b61f-45aa-a0de-bb6e1c5d34cb","order_by":0,"name":"Shubham Modgil","email":"","orcid":"","institution":"Punjab Engineering College","correspondingAuthor":false,"prefix":"","firstName":"Shubham","middleName":"","lastName":"Modgil","suffix":""},{"id":592075324,"identity":"f7005045-e2d1-4a8f-9023-463853addfd2","order_by":1,"name":"Mukul Kumar","email":"","orcid":"","institution":"Punjab Engineering College","correspondingAuthor":false,"prefix":"","firstName":"Mukul","middleName":"","lastName":"Kumar","suffix":""},{"id":592075325,"identity":"57e53b16-c32e-4b64-bd99-ff86421b5951","order_by":2,"name":"Arun Kumar Singh","email":"","orcid":"","institution":"Punjab Engineering College","correspondingAuthor":false,"prefix":"","firstName":"Arun","middleName":"Kumar","lastName":"Singh","suffix":""},{"id":592075326,"identity":"6f4698c8-89b6-4e65-8d39-a22378b93db7","order_by":3,"name":"Shobhna Dhiman","email":"","orcid":"","institution":"Punjab Engineering College","correspondingAuthor":false,"prefix":"","firstName":"Shobhna","middleName":"","lastName":"Dhiman","suffix":""},{"id":592075327,"identity":"20a391a1-5fb7-4d77-bf65-0d506d708ce4","order_by":4,"name":"Gyaneshwar Sharma","email":"","orcid":"","institution":"Tilak Dhari Post Graduate College","correspondingAuthor":false,"prefix":"","firstName":"Gyaneshwar","middleName":"","lastName":"Sharma","suffix":""},{"id":592075328,"identity":"5a435f91-fd40-4777-bac4-dee503ebd527","order_by":5,"name":"O.P. Thakur","email":"","orcid":"","institution":"Solid State Physics Laboratory","correspondingAuthor":false,"prefix":"","firstName":"O.P.","middleName":"","lastName":"Thakur","suffix":""},{"id":592075329,"identity":"71d563eb-1c38-4464-8aa7-09f3769dfd96","order_by":6,"name":"Sanjeev Kumar","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA00lEQVRIiWNgGAWjYJACAyCWgzDZwIg4LcakaQGBxAaYFoJAvv3sgYIPFYfTt7M3P2D4UHaYgU+6gYCjzuQlGM44czh3Z88xA8YZ5w4zsMkcIKCFIcfAmLctLXfDjRwGZt42oBaJBAIO639jYPz3X1q6wf03DMx/idHCcANoC2ODTYLBDR4GZkZitBjceGNg2HPMxnBnT5rBwZ5z6TxEOCzHzOBHjYS8Ofvhhw9+lFnLyc8g5DBgXBiArQPiA0DMQ1A9EDA/gGkZBaNgFIyCUYAVAACzCz8UuPZZaAAAAABJRU5ErkJggg==","orcid":"","institution":"Punjab Engineering College","correspondingAuthor":true,"prefix":"","firstName":"Sanjeev","middleName":"","lastName":"Kumar","suffix":""}],"badges":[],"createdAt":"2026-02-06 12:40:46","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8807205/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8807205/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10854-026-17174-3","type":"published","date":"2026-04-08T15:58:32+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":106810293,"identity":"0b66f0bc-f45f-4397-a40d-13caaba9cbf1","added_by":"auto","created_at":"2026-04-13 16:15:18","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":8979362,"visible":true,"origin":"","legend":"","description":"","filename":"Manuscript34.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8807205/v1_covered_5fd43afc-bbe4-4dff-bcb3-d2d97829657f.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Multifunctional Pyroelectric and Electrocaloric response through Eu3+ doping in 0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3 ceramics at Morphotropic Phase Boundary","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"PNN-PZ-PT, Morphotropic phase boundary, ferroelectric, electrocaloric, pyroelectric","lastPublishedDoi":"10.21203/rs.3.rs-8807205/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8807205/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study presents a strategy to enhance the pyroelectric and electrocaloric responses at room temperature by tailoring the Landau free-energy landscape of a ternary morphotropic phase boundary (MPB) composition 0.55Pb(Ni\u003csub\u003e1/3\u003c/sub\u003eNb\u003csub\u003e2/3\u003c/sub\u003e)O\u003csub\u003e3\u003c/sub\u003e-0.135PbZrO\u003csub\u003e3\u003c/sub\u003e-0.315PbTiO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;xEu\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (x\u0026thinsp;=\u0026thinsp;0, 0.01 \u0026amp; 0.02). Eu\u003csup\u003e3+\u003c/sup\u003e substitution at the A-site reduces the effective ionic spacing, inducing octahedral tilting and stabilizing a lower-symmetry crystal structure, predominantly rhombohedral, in the vicinity of room temperature. The associated local lattice distortion and charge imbalance promote relaxor behaviour in the PNN-PZ-PT system. A pronounced enhancement in pyroelectric performance is observed for the x\u0026thinsp;=\u0026thinsp;0.02 composition, with the pyroelectric coefficient reaching\u0026thinsp;~\u0026thinsp;33.34 \u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003eC/m\u003csup\u003e2\u003c/sup\u003eK and the corresponding pyroelectric figures of merits (FOMs) attain values of \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{F}_{i}\\)\u003c/span\u003e\u003c/span\u003e ~ 1993 pm/V, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{F}_{v}\\)\u003c/span\u003e\u003c/span\u003e ~ 0.01592 m\u003csup\u003e2\u003c/sup\u003e/C, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{F}_{d}\\)\u003c/span\u003e\u003c/span\u003e ~23.57 \u0026micro;(Pa)\u003csup\u003e\u0026minus;0.5\u003c/sup\u003e, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{F}_{e}\\)\u003c/span\u003e\u003c/span\u003e ~107 Jm\u003csup\u003e3\u003c/sup\u003e/K and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{F}_{e}^{*}\\)\u003c/span\u003e\u003c/span\u003e ~26.48 pm\u003csup\u003e3\u003c/sup\u003e/N. Notably, electrocaloric measurements reveal the emergence of an orthorhombic phase near room temperature, resulting in an improved electrocaloric temperature change. Concurrently, Eu\u003csup\u003e3+\u003c/sup\u003e doping suppresses the inverse piezoelectric coefficient (\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{d}_{33}^{*}\\)\u003c/span\u003e\u003c/span\u003e) from 1036 pm/V for x = 0 to 460 pm/V for x = 0.02 sample indicating reduced electromechanical coupling, while the energy storage density exhibits an improvement near the ferroelectric-paraelectric phase transition. These findings demonstrate that Eu\u003csup\u003e3+\u003c/sup\u003emodified PNN-PZ-PT ceramics offer a tunable multifunctional platform with potential applications in solid-state cooling, infrared detection, and thermal energy harvesting.\u003c/p\u003e","manuscriptTitle":"Multifunctional Pyroelectric and Electrocaloric response through Eu3+ doping in 0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3 ceramics at Morphotropic Phase Boundary","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-18 06:42:28","doi":"10.21203/rs.3.rs-8807205/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"de545947-78f6-4427-ad18-30ded12a53cc","owner":[],"postedDate":"February 18th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-04-13T16:11:07+00:00","versionOfRecord":{"articleIdentity":"rs-8807205","link":"https://doi.org/10.1007/s10854-026-17174-3","journal":{"identity":"journal-of-materials-science-materials-in-electronics","isVorOnly":false,"title":"Journal of Materials Science: Materials in Electronics"},"publishedOn":"2026-04-08 15:58:32","publishedOnDateReadable":"April 8th, 2026"},"versionCreatedAt":"2026-02-18 06:42:28","video":"","vorDoi":"10.1007/s10854-026-17174-3","vorDoiUrl":"https://doi.org/10.1007/s10854-026-17174-3","workflowStages":[]},"version":"v1","identity":"rs-8807205","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8807205","identity":"rs-8807205","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}