Selective synthesis of pure CsPbBr3 and pure Cs4PbBr6 nanocrystals towards the fine control of their emission properties

Selective synthesis of pure CsPbBr3 and pure Cs4PbBr6 nanocrystals towards the fine control of their emission properties | 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 Selective synthesis of pure CsPbBr3 and pure Cs4PbBr6 nanocrystals towards the fine control of their emission properties Svetlana Siprova, Vincenzo Caligiuri, Attilio Golemme, Roberto Termine, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8742423/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 8 You are reading this latest preprint version Abstract Perovskite nanocrystals (NCs) have garnered significant attention owing to their remarkable optoelectronic properties, making them promising candidates for various applications such as light-emitting diodes, photodetectors, and solar cells. Among perovskite NCs, cesium lead halide (CsPbX 3 ) and tetracesium lead hexahalide (Cs 4 PbX 6 ) are of particular interest due to their tunable bandgap and excellent photoluminescence characteristics. Herein, we present a comparative study on the selective synthesis of CsPbBr 3 and Cs 4 PbBr 6 NCs, elucidating the distinct reaction pathways, controlling parameters governing their formation and unveil the non-luminescent properties of pure Cs 4 PbBr 6 nanocrystals. We employ a facile hot-injection method utilizing benzoyl bromide as a unique bromide source, to synthesize both CsPbBr 3 and Cs 4 PbBr 6 NCs. Through systematic variation of precursor ratios and reaction temperature, we achieve precise control over nanocrystal morphology, crystallinity and phase purity. A detailed structural characterization reveals the formation of well-defined CsPbBr 3 and Cs 4 PbBr 6 NCs and highlights the importance of combining complementary techniques to unambiguously identify the crystalline phase. Optical investigations show that phase-pure Cs 4 PbBr 6 NCs synthesized at low injection temperatures are intrinsically non-emissive, whereas samples obtained at higher injection temperatures exhibit weak emission with spectral features resembling those of CsPbBr 3 NCs, particularly after thermal annealing. Thermal annealing of NC thin films enhances their adhesion to the substrate, enabling potential multilayer fabrication and inducing slight shifts in the emission spectra. Notably, we extended our synthesis methodology to the selective synthesis of cesium lead chloride (CsPbCl 3 ) and tetracesium lead hexachloride (Cs 4 PbCl 6 ) NCs using benzoyl chloride, demonstrating the versatility and reproducibility of the synthetic pathway. Halide perovskites CsPbBr3 Cs4PbBr6 nanocrystals photoluminescence Full Text Additional Declarations No competing interests reported. Supplementary Files SuppInfosynthesis.docx Cite Share Download PDF Status: Under Review Version 1 posted Reviews received at journal 25 Mar, 2026 Reviews received at journal 13 Mar, 2026 Reviewers agreed at journal 13 Mar, 2026 Reviewers agreed at journal 18 Feb, 2026 Reviewers invited by journal 18 Feb, 2026 Editor assigned by journal 17 Feb, 2026 Submission checks completed at journal 16 Feb, 2026 First submitted to journal 16 Feb, 2026 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. 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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-8742423","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":593646049,"identity":"46455300-a3a9-4906-9ebd-d8d06e4c7d38","order_by":0,"name":"Svetlana 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14:55:35","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8742423/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8742423/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":103050547,"identity":"a8853624-e515-4714-8249-8ecf1d4ea485","added_by":"auto","created_at":"2026-02-20 07:50:30","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1917632,"visible":true,"origin":"","legend":"","description":"","filename":"papersynthesis16022026.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8742423/v1_covered_dfa6e84e-635a-494c-a4ab-10b70e4f6153.pdf"},{"id":103047232,"identity":"2fec839d-fecc-49d9-9f7f-ab5b5532c38f","added_by":"auto","created_at":"2026-02-20 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properties","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"discover-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dime","sideBox":"Learn more about [Discover Materials](https://www.springer.com/journal/43939)","snPcode":"","submissionUrl":"","title":"Discover Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Halide perovskites, CsPbBr3, Cs4PbBr6, nanocrystals, photoluminescence","lastPublishedDoi":"10.21203/rs.3.rs-8742423/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8742423/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePerovskite nanocrystals (NCs) have garnered significant attention owing to their remarkable optoelectronic properties, making them promising candidates for various applications such as light-emitting diodes, photodetectors, and solar cells. Among perovskite NCs, cesium lead halide (CsPbX\u003csub\u003e3\u003c/sub\u003e) and tetracesium lead hexahalide (Cs\u003csub\u003e4\u003c/sub\u003ePbX\u003csub\u003e6\u003c/sub\u003e) are of particular interest due to their tunable bandgap and excellent photoluminescence characteristics. Herein, we present a comparative study on the selective synthesis of CsPbBr\u003csub\u003e3\u003c/sub\u003e and Cs\u003csub\u003e4\u003c/sub\u003ePbBr\u003csub\u003e6\u003c/sub\u003e NCs, elucidating the distinct reaction pathways, controlling parameters governing their formation and unveil the non-luminescent properties of pure Cs\u003csub\u003e4\u003c/sub\u003ePbBr\u003csub\u003e6\u003c/sub\u003e nanocrystals. We employ a facile hot-injection method utilizing benzoyl bromide as a unique bromide source, to synthesize both CsPbBr\u003csub\u003e3\u003c/sub\u003e and Cs\u003csub\u003e4\u003c/sub\u003ePbBr\u003csub\u003e6\u003c/sub\u003e NCs. Through systematic variation of precursor ratios and reaction temperature, we achieve precise control over nanocrystal morphology, crystallinity and phase purity. A detailed structural characterization reveals the formation of well-defined CsPbBr\u003csub\u003e3\u003c/sub\u003e and Cs\u003csub\u003e4\u003c/sub\u003ePbBr\u003csub\u003e6\u003c/sub\u003e NCs and highlights the importance of combining complementary techniques to unambiguously identify the crystalline phase. Optical investigations show that phase-pure Cs\u003csub\u003e4\u003c/sub\u003ePbBr\u003csub\u003e6\u003c/sub\u003e NCs synthesized at low injection temperatures are intrinsically non-emissive, whereas samples obtained at higher injection temperatures exhibit weak emission with spectral features resembling those of CsPbBr\u003csub\u003e3\u003c/sub\u003e NCs, particularly after thermal annealing. Thermal annealing of NC thin films enhances their adhesion to the substrate, enabling potential multilayer fabrication and inducing slight shifts in the emission spectra. Notably, we extended our synthesis methodology to the selective synthesis of cesium lead chloride (CsPbCl\u003csub\u003e3\u003c/sub\u003e) and tetracesium lead hexachloride (Cs\u003csub\u003e4\u003c/sub\u003ePbCl\u003csub\u003e6\u003c/sub\u003e) NCs using benzoyl chloride, demonstrating the versatility and reproducibility of the synthetic pathway.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Selective synthesis of pure CsPbBr3 and pure Cs4PbBr6 nanocrystals towards the fine control of their emission properties","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-20 06:53:02","doi":"10.21203/rs.3.rs-8742423/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"editorInvitedReview","content":"","date":"2026-03-25T17:05:32+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-03-13T15:03:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"303016528191854899619412451192549502962","date":"2026-03-13T14:29:46+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"7313692134793048951730344504716691036","date":"2026-02-18T08:19:06+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-02-18T07:58:24+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-02-17T05:21:40+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-02-16T12:03:33+00:00","index":"","fulltext":""},{"type":"submitted","content":"Discover Materials","date":"2026-02-16T11:59:11+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"discover-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dime","sideBox":"Learn more about [Discover Materials](https://www.springer.com/journal/43939)","snPcode":"","submissionUrl":"","title":"Discover Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"f0526fab-817b-4a69-b06a-89ebc6597502","owner":[],"postedDate":"February 20th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-02-20T06:53:02+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-20 06:53:02","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8742423","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8742423","identity":"rs-8742423","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}