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Understanding the role of zinc dithiocarbamate complexes as single source precursors to ZnS nanomaterials

Islam, HU; Roffey, A; Hollingsworth, N; Bras, W; Sankar, G; De Leeuw, NH; Hogarth, G; (2020) Understanding the role of zinc dithiocarbamate complexes as single source precursors to ZnS nanomaterials. Nanoscale Advances , 2 (2) pp. 798-807. 10.1039/c9na00665f. Green open access

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Abstract

Zinc sulfide is an important wide-band gap semi-conductor and dithiocarbamate complexes [Zn(S2CNR2)2] find widespread use as single-source precursors for the controlled synthesis of ZnS nanoparticulate modifications. Decomposition of [Zn(S2CNiBu2)2] in oleylamine gives high aspect ratio wurtzite nanowires, the average length of which was increased upon addition of thiuram disulfide to the decomposition mixture. To provide further insight into the decomposition process, X-ray absorption spectroscopy (XAS) of [Zn(S2CNMe2)2] was performed in the solid-state, in non-coordinating xylene and in oleylamine. In the solid-state, dimeric [Zn(S2CNMe2)2]2 was characterised in accord with the single crystal X-ray structure, while in xylene this breaks down into tetrahedral monomers. In situ XAS in oleylamine (RNH2) shows that the coordination sphere is further modified, amine binding to give five-coordinate [Zn(S2CNMe2)2(RNH2)]. This species is stable to ca. 70 °C, above which amine dissociates and at ca. 90 °C decomposition occurs to generate ZnS. The relatively low temperature onset of nanoparticle formation is associated with amine-exchange leading to the in situ formation of [Zn(S2CNMe2)(S2CNHR)] which has a low temperature decomposition pathway. Combining these observations with the previous work of others allows us to propose a detailed mechanistic scheme for the overall process.

Type: Article
Title: Understanding the role of zinc dithiocarbamate complexes as single source precursors to ZnS nanomaterials
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/c9na00665f
Publisher version: https://doi.org/10.1039/c9na00665f
Language: English
Additional information: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence (http://creativecommons.org/licenses/by-nc/3.0/).
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10105052
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