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      Formation of colloidal alloy semiconductor CdTeSe magic-size clusters at room temperature

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          Abstract

          Alloy semiconductor magic-size clusters (MSCs) have received scant attention and little is known about their formation pathway. Here, we report the synthesis of alloy CdTeSe MSC-399 (exhibiting sharp absorption peaking at 399 nm) at room temperature, together with an explanation of its formation pathway. The evolution of MSC-399 at room temperature is detected when two prenucleation-stage samples of binary CdTe and CdSe are mixed, which are transparent in optical absorption. For a reaction consisting of Cd, Te, and Se precursors, no MSC-399 is observed. Synchrotron-based in-situ small angle X-ray scattering (SAXS) suggests that the sizes of the two samples and their mixture are similar. We argue that substitution reactions take place after the two binary samples are mixed, which result in the formation of MSC-399 from its precursor compound (PC-399). The present study provides a room-temperature avenue to engineering alloy MSCs and an in-depth understanding of their probable formation pathway.

          Abstract

          Alloy magic-size clusters (MSCs) are difficult to synthesize, in part because so little is known about how they form. Here, the authors produce single-ensemble alloy CdTeSe MSCs at room temperature by mixing prenucleation-stage solutions of CdTe and CdSe, uncovering a formation pathway that may extend to the synthesis of other alloy MSCs.

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          Formation of high-quality CdTe, CdSe, and CdS nanocrystals using CdO as precursor.

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            Cation exchange reactions in ionic nanocrystals.

            Cation exchange has been investigated in a wide range of nanocrystals of varying composition, size, and shape. Complete and fully reversible exchange occurs, and the rates of the reactions are much faster than in bulk cation exchange processes. A critical size has been identified below which the shapes of complex nanocrystals evolve toward the equilibrium shape with lowest energy during the exchange reaction. Above the critical size, the anion sublattice remains intact and the basic shapes of the initial nanocrystals are retained throughout the cation exchange. The size-dependent shape change can also be used to infer features of the microscopic mechanism.
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              Ab initio random structure searching.

              It is essential to know the arrangement of the atoms in a material in order to compute and understand its properties. Searching for stable structures of materials using first-principles electronic structure methods, such as density-functional-theory (DFT), is a rapidly growing field. Here we describe our simple, elegant and powerful approach to searching for structures with DFT, which we call ab initio random structure searching (AIRSS). Applications to discovering the structures of solids, point defects, surfaces, and clusters are reviewed. New results for iron clusters on graphene, silicon clusters, polymeric nitrogen, hydrogen-rich lithium hydrides, and boron are presented.
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                Author and article information

                Contributors
                zengjianrong@sinap.ac.cn
                mengzhang@scu.edu.cn
                kuiyu@scu.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                11 April 2019
                11 April 2019
                2019
                : 10
                : 1674
                Affiliations
                [1 ]ISNI 0000 0001 0807 1581, GRID grid.13291.38, Institute of Atomic and Molecular Physics, , Sichuan University, ; 610065 Chengdu, P. R. China
                [2 ]ISNI 0000 0004 0449 7958, GRID grid.24433.32, Metrology Research Centre, , National Research Council of Canada, ; Ottawa, ON K1A 0R6 Canada
                [3 ]ISNI 0000 0001 2171 1133, GRID grid.4868.2, School of Physics and Astronomy, , Queen Mary University of London, ; London, E1 4NS UK
                [4 ]ISNI 0000 0001 0807 1581, GRID grid.13291.38, School of Physical Science and Technology, , Sichuan University, ; 610065 Chengdu, P. R. China
                [5 ]ISNI 0000 0001 0807 1581, GRID grid.13291.38, Engineering Research Center in Biomaterials, , Sichuan University, ; 610065 Chengdu, P. R. China
                [6 ]ISNI 0000 0001 0807 1581, GRID grid.13291.38, Analytical & Testing Center, , Sichuan University, ; 610065 Chengdu, P. R. China
                [7 ]ISNI 0000 0004 1757 641X, GRID grid.440665.5, Jilin Ginseng Academy, , Changchun University of Chinese Medicine, ; 130117 Changchun, P. R. China
                [8 ]ISNI 0000000119573309, GRID grid.9227.e, Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, , Chinese Academy of Sciences, ; 201204 Shanghai, P. R. China
                [9 ]ISNI 0000000119573309, GRID grid.9227.e, Shanghai Institute of Applied Physics, , Chinese Academy of Sciences, ; 201800 Shanghai, P. R. China
                [10 ]ISNI 0000 0001 0807 1581, GRID grid.13291.38, State Key Laboratory of Polymer Materials Engineering, , Sichuan University, ; 610065 Chengdu, P. R. China
                Author information
                http://orcid.org/0000-0003-2326-5338
                http://orcid.org/0000-0002-2852-2527
                Article
                9705
                10.1038/s41467-019-09705-w
                6459852
                30976002
                efa9e0a7-f6d0-489c-a2de-8c29e01c05f8
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 8 October 2018
                : 22 March 2019
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