Robust synthesis of two-dimensional metal dichalcogenides and their alloys by active chalcogen monomer supply | 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 Physical Sciences - Article Robust synthesis of two-dimensional metal dichalcogenides and their alloys by active chalcogen monomer supply Kaihui Liu, Yonggang Zuo, Can Liu, Liping Ding, Ruixi Qiao, Chang Liu, and 13 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-411823/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Two-dimensional (2D) transition metal dichalcogenides (TMDs), with their atomic thicknesses, high carrier mobility, fast charge transfer, and intrinsic spin-valley couplings, have been demonstrated one of the most appealing candidates for next-generation electronic and optoelectronic devices. The synthesis of TMDs with well-controlled crystallinity, quality and composition is essential to fully realize their promising applications. Similar to that in III-V semiconductor synthesis, the precise precursor supply is a precondition for controllable growth of TMDs. Although great efforts have been devoted to modulate the transition metal supply, few effective methods of chalcogen feeding control were developed. Herein we report a strategy of using active chalcogen monomer supply to grow TMDs and their alloys in a robust and controllable manner. It is found that at a high temperature, the active chalcogen monomers (such as S, Se, Te atoms or their mixtures) can be controllably released from metal chalcogenides and, thus, enable the synthesis of TMDs (MX 2 , M = Mo, W; X = S, Se, Te) with very high quality, e.g., MoS 2 monolayers exhibit photoluminescent circular helicity of ~92%, comparable to the best exfoliated single-crystal flakes and close to the theoretical limit of unity. More intriguingly, a uniform quaternary TMD alloy with three different anions, i.e., MoS 2(1-x-y) Se 2x Te 2y , was accomplished for the first time. Our mechanism study revealed that the active chalcogen monomers can bind and diffuse freely on a TMD surface, which enables the effective nucleation and reaction, quick chalcogen vacancy healing, and alloy formation during the growth. The chalcogen monomer supply strategy offers more degrees of freedom for the controllable synthesis of 2D compounds and their alloys, which will greatly benefit the development of high-end devices with desired 2D materials. Materials Engineering Materials Chemistry Nanoscience Hard Condensed-matter Physics Soft Condensed-matter Physics Two-dimensional transition metal dichalcogenides alloys chalcogen monomers supply Figures Figure 1 Figure 2 Figure 3 Figure 4 Full Text Additional Declarations There is NO Competing Interest. Cite Share Download PDF Status: Posted 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-411823","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Physical Sciences - Article","associatedPublications":[],"authors":[{"id":20873423,"identity":"7e5d9d0c-c12f-40fe-81cc-74ec4bef60aa","order_by":0,"name":"Kaihui Liu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAuElEQVRIiWNgGAWjYBACCQnmhgMMFQwGYA6RWhiBWs6QqoWBsY0ULZKzGxsP8867Y2xwgPngbR4GuzyCWqRlDjYc5t32zMzgAFuyNQ9DcjFBLXISiSAth20MDvCYSfMwHEhsIE7LHJAW/m/EaZEGa2k4DHQYDxtxWiRnJDYcnHPsmbHkYTZjyzkGyYS1SNxIPvzhTc0dw77jzQ9vvKmwI6wFCg4wMDCDaAMi1UO0jIJRMApGwSjABQBiAT2twsGsYQAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0002-8781-2495","institution":"State Key Laboratory for Mesoscopic Physics, Frontiers Science Center for Nano-optoelectronics, School of Physics, Peking University, Beijing 100871","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Kaihui","middleName":"","lastName":"Liu","suffix":""},{"id":20873424,"identity":"90c0806e-2b5b-4813-b857-53bf9a1be302","order_by":1,"name":"Yonggang Zuo","email":"","orcid":"https://orcid.org/0000-0003-1262-6767","institution":"Institute of Physics, Chinese Academy of Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yonggang","middleName":"","lastName":"Zuo","suffix":""},{"id":20873425,"identity":"db319828-c2b0-4a67-9936-143d572097ba","order_by":2,"name":"Can Liu","email":"","orcid":"https://orcid.org/0000-0001-5451-4144","institution":"State Key Laboratory for Mesoscopic Physics, Frontiers Science Centre for Nanooptoelectronics, School of Physics, Peking University, Beijing, China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Can","middleName":"","lastName":"Liu","suffix":""},{"id":20873426,"identity":"51ddd50f-5b6c-4c97-b476-fa6fa00f41ab","order_by":3,"name":"Liping Ding","email":"","orcid":"","institution":"Institute for Basic Science","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Liping","middleName":"","lastName":"Ding","suffix":""},{"id":20873427,"identity":"5f9f08a1-cadb-4c91-8edf-b6eecdda1431","order_by":4,"name":"Ruixi Qiao","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Ruixi","middleName":"","lastName":"Qiao","suffix":""},{"id":20873428,"identity":"6d88a818-636d-4ca6-8b86-ddb15c93cb22","order_by":5,"name":"Chang Liu","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Chang","middleName":"","lastName":"Liu","suffix":""},{"id":20873429,"identity":"8c5fdd20-0642-4c78-9034-d85759d170db","order_by":6,"name":"Ying Fu","email":"","orcid":"","institution":"Institute of Physics, Chinese Academy of Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Ying","middleName":"","lastName":"Fu","suffix":""},{"id":20873430,"identity":"6f47be19-e2ab-4c28-98c8-41067807dfcc","order_by":7,"name":"Kehai Liu","email":"","orcid":"","institution":"Institute of Physics, Chinese Academy of Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Kehai","middleName":"","lastName":"Liu","suffix":""},{"id":20873431,"identity":"ebe33616-58ba-4360-ae80-470f652df094","order_by":8,"name":"Xu Zhou","email":"","orcid":"https://orcid.org/0000-0003-3318-8735","institution":"South China Normal University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Xu","middleName":"","lastName":"Zhou","suffix":""},{"id":20873432,"identity":"c2e35649-4dec-4962-865e-3cabf8b7ec6e","order_by":9,"name":"Qinghe Wang","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Qinghe","middleName":"","lastName":"Wang","suffix":""},{"id":20873433,"identity":"10bccbaf-4f16-40e0-b546-cc275a7e0645","order_by":10,"name":"Quanlin Guo","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Quanlin","middleName":"","lastName":"Guo","suffix":""},{"id":20873434,"identity":"465d6789-af51-4f49-8ec5-a6566f808802","order_by":11,"name":"Guodong Xue","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Guodong","middleName":"","lastName":"Xue","suffix":""},{"id":20873435,"identity":"242e4847-dcc0-48d0-b25b-9c2002d80a0d","order_by":12,"name":"Jinhuan Wang","email":"","orcid":"","institution":"Beijing Institute of Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Jinhuan","middleName":"","lastName":"Wang","suffix":""},{"id":20873436,"identity":"5f47a571-c1cb-48e3-a20c-7b6566563cff","order_by":13,"name":"Hao Hong","email":"","orcid":"","institution":"State Key Laboratory for Mesoscopic Physics, Collaborative Innovation Centre of Quantum Matter, School of Physics, Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Hao","middleName":"","lastName":"Hong","suffix":""},{"id":20873437,"identity":"7e377b31-6f06-437f-8436-f242c0e97b0b","order_by":14,"name":"Muhong Wu","email":"","orcid":"https://orcid.org/0000-0003-3607-8945","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Muhong","middleName":"","lastName":"Wu","suffix":""},{"id":20873438,"identity":"f51c28ff-5161-42f2-bcfd-6276ccc9de66","order_by":15,"name":"Dapeng Yu","email":"","orcid":"","institution":"Institute for Quantum Science and Engineering and Department of Physics, South University of Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Dapeng","middleName":"","lastName":"Yu","suffix":""},{"id":20873439,"identity":"16dd1189-46ea-4868-a350-2d65e9b39d58","order_by":16,"name":"Enge Wang","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Enge","middleName":"","lastName":"Wang","suffix":""},{"id":20873440,"identity":"1376288a-6d45-4b86-91c1-2078c1b771de","order_by":17,"name":"Xuedong Bai","email":"","orcid":"https://orcid.org/0000-0002-1403-491X","institution":"Institute of Physics, Chinese Academy of Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Xuedong","middleName":"","lastName":"Bai","suffix":""},{"id":20873441,"identity":"d159f60d-7f97-4749-b606-452040ad12b1","order_by":18,"name":"Feng Ding","email":"","orcid":"https://orcid.org/0000-0001-9153-9279","institution":"Institute for Basic Science","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Feng","middleName":"","lastName":"Ding","suffix":""}],"badges":[],"createdAt":"2021-04-11 14:20:46","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-411823/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-411823/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":8287265,"identity":"7723a6fa-14a2-43dc-8276-7e82e977706f","added_by":"auto","created_at":"2021-04-21 16:11:14","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":187872,"visible":true,"origin":"","legend":"Growth of high-quality monolayer MoS2 by sulfur monomer supply. a, Schematic\nof sulfur (S) monomer supply for the growth of MoS2. S monomers are released from the surface\n of ZnS under high temperature, then confined in the narrow space and react with Na2MoO4 to\n from MoS2. b, In-situ mass spectrum of ZnS annealed at 1000 ℃. The intense peak at the mass\n of 32 clearly proves the dominating release of S monomers. The measurements were carried out\n with carrier gas of He and the data was subtracted by background. c, Optical image of as-grown\n monolayer MoS2 domain on sapphire. d, Atomic-resolved HAADF-STEM image of the prepared\n MoS2, revealing the high crystallinity of MoS2 without detectable S vacancies. e, Low\ntemperature (10 K) PL spectra of MoS2 samples fed by S monomer (orange curve) and S powder\n (dark yellow curve), respectively. Three typical features, X0, XT, and XD peaks assign to neutral\n exciton, trion, and defect state emission peaks, respectively. The absence of XD peak confirmed\n the high quality of MoS2 grown by S monomer supply. f, The circular dichroism PL spectrum measured at 10 K. The near-unity polarization of MoS2 on sapphire indicates the high optical quality.","description":"","filename":"Fig1.png","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1/92bbcfcb3aff5045f0f5a250.png"},{"id":8287267,"identity":"57018bbe-1bc3-4c83-ace8-7a433f617b58","added_by":"auto","created_at":"2021-04-21 16:11:14","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":228267,"visible":true,"origin":"","legend":"Universal growth of diverse TMDs by chalcogen monomer supply. a, Optical\n images of the representative TMDs, including 2H phase MoS2, MoSe2, MoTe2, WS2, WSe2 and\n 1T’ phase WTe2. b, The calculated formation energy (Ef) of the six representative TMDs. When\n chalcogen bulks are supplied as precursors, the formation of transition metal tellurides in relative\n to their corresponding sulphide and selenide are less favourable due to their high formation\n energy (-0.73 and -0.68 eV/unit for MoTe2 and WTe2, respectively). While it becomes highly favourable when Te monomers are applied. c-e, The corresponding Raman (c,d) and PL (e) spectra of TMDs in (a). All spectra were vertically shifted for clarity.","description":"","filename":"Fig2.png","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1/68b69cb2832822009614bbaa.png"},{"id":8287266,"identity":"62c9c632-0886-4f49-8ad2-54c16f5a6c99","added_by":"auto","created_at":"2021-04-21 16:11:14","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":449985,"visible":true,"origin":"","legend":"Growth and characterization of quaternary TMD alloy. a, Schematic diagram of\nquaternary alloy growth using a compressed plate mixed with chalcogenide powders of ZnS,\n ZnSe, and ZnTe. b, Optical image of MoS2(1-x-y)Se2xTe2y domain on SiO2/Si substrate. c,d, PL (c)\n and Raman (d) spectra of the MoS2(1-x-y)Se2xTe2y sample grown at different temperatures. As the\n growth temperature increased, the PL peak position showed a clear red shift. The intensity of\n MoS2-like E2g (~380 cm-1) and A1g (~400 cm-1) was reduced while the MoTe2-like A1g (~150 cm-\n 1) increased and MoSe2-like A1g (~240 cm-1) increased first and then reduced. e,f, STEM images\n of the MoS2(1-x-y)Se2xTe2y, demonstrating the high crystallinity of quaternary alloy. g, Intensity\n profiles along the labeled orange dotted box in (f), which highlights the occupancies of Mo, S,\n Se, and Te sites. h, The Te-site distribution in a 32 × 32 nm STEM image of the quaternary alloy.\n The image was divided into 30 × 30 parts. i, The corresponding statistical histogram of Te-site counts in each parts of the image. It shows a well binomial distribution feature (purple dotted line), revealing the random distribution of Te atoms.","description":"","filename":"Fig3.png","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1/be289b36efc928762cebdf93.png"},{"id":8286947,"identity":"2a4610a6-f6ef-4ed6-ab8d-7a94fae520e5","added_by":"auto","created_at":"2021-04-21 16:08:14","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":93513,"visible":true,"origin":"","legend":"Growth Mechanism with chalcogen monomer supply in MoX2 (X = S, Se, Te). a,\n Schematic diagram of adsorption, diffusion, and vacancy healing of chalcogen monomer on\n MoX2 surface. b, The binding energies of monomers and dimers on MoX2 surface. The much\n higher energy of monomers facilitates their better adsorption on the TMD surface than dimers. c,\n The energy profiles of vacancy healing for MoX2 surface by using chalcogen monomers. The relatively small energy barriers of chalcogen monomer diffusion and the highly exothermic reaction at the vacancy both accelerate the self-healing of MoX2.","description":"","filename":"Fig4.png","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1/d6a7170e7f0a0384b1aeb341.png"},{"id":13623781,"identity":"f9392ee3-f488-4725-a6e0-4c669290de3b","added_by":"auto","created_at":"2021-09-17 07:19:55","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4600618,"visible":true,"origin":"","legend":"","description":"","filename":"text.pdf","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1_covered.pdf"},{"id":9331989,"identity":"f05e1255-d455-4a0b-9c0a-3c742fce5b92","added_by":"auto","created_at":"2021-05-19 09:26:22","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4597073,"visible":true,"origin":"","legend":"","description":"","filename":"text.pdf","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1_covered.pdf"},{"id":8287472,"identity":"483da510-6608-425d-8b11-a081f25c2270","added_by":"auto","created_at":"2021-04-21 16:14:20","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4442253,"visible":true,"origin":"","legend":"","description":"","filename":"text.pdf","url":"https://assets-eu.researchsquare.com/files/rs-411823/v1_stamped.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Robust synthesis of two-dimensional metal dichalcogenides and their alloys by active chalcogen monomer supply","fulltext":[{"header":"Full Text","content":"This preprint is available for \u003ca href='/article/rs-411823/latest.pdf' target='_blank'\u003edownload as a PDF\u003c/a\u003e."}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"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":"Two-dimensional transition metal dichalcogenides, alloys, chalcogen monomers supply","lastPublishedDoi":"10.21203/rs.3.rs-411823/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-411823/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Two-dimensional (2D) transition metal dichalcogenides (TMDs), with their atomic thicknesses, high carrier mobility, fast charge transfer, and intrinsic spin-valley couplings, have been demonstrated one of the most appealing candidates for next-generation electronic and optoelectronic devices. The synthesis of TMDs with well-controlled crystallinity, quality and composition is essential to fully realize their promising applications. Similar to that in III-V semiconductor synthesis, the precise precursor supply is a precondition for controllable growth of TMDs. Although great efforts have been devoted to modulate the transition metal supply, few effective methods of chalcogen feeding control were developed. Herein we report a strategy of using active chalcogen monomer supply to grow TMDs and their alloys in a robust and controllable manner. It is found that at a high temperature, the active chalcogen monomers (such as S, Se, Te atoms or their mixtures) can be controllably released from metal chalcogenides and, thus, enable the synthesis of TMDs (MX\u003csub\u003e2\u003c/sub\u003e, M = Mo, W; X = S, Se, Te) with very high quality, e.g., MoS\u003csub\u003e2\u003c/sub\u003e monolayers exhibit photoluminescent circular helicity of ~92%, comparable to the best exfoliated single-crystal flakes and close to the theoretical limit of unity. More intriguingly, a uniform quaternary TMD alloy with three different anions, i.e., MoS\u003csub\u003e2(1-x-y)\u003c/sub\u003eSe\u003csub\u003e2x\u003c/sub\u003eTe\u003csub\u003e2y\u003c/sub\u003e, was accomplished for the first time. Our mechanism study revealed that the active chalcogen monomers can bind and diffuse freely on a TMD surface, which enables the effective nucleation and reaction, quick chalcogen vacancy healing, and alloy formation during the growth. The chalcogen monomer supply strategy offers more degrees of freedom for the controllable synthesis of 2D compounds and their alloys, which will greatly benefit the development of high-end devices with desired 2D materials.","manuscriptTitle":"Robust synthesis of two-dimensional metal dichalcogenides and their alloys by active chalcogen monomer supply","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2021-04-21 16:08:12","doi":"10.21203/rs.3.rs-411823/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"
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